Metal complex and organic letroluminescent devices

ABSTRACT

A metal complex which has a metal complex structure showing light emission from triplet excited state, and has a monovalent group derived from carbazole, and a light-emitting device using said metal complex.

TECHNICAL FIELD

The present invention relates to a new metal complex, and alight-emitting device using said metal complex as a light-emittingsubstance.

BACKGROUND ART

As the light-emitting material having phosphorescence in visible regionused for a light emitting layer of light-emitting device, devices usinga metal complex (hereafter may be referred to as triplet light-emittingcomplex) showing light emission from triplet excited state have beenknown.

As the triplet light-emitting complex, for example, Ir(ppy)3 whichincludes iridium as the central metal, (Appl. Phys. Lett., 75, 4(1999)),PtOEP which includes platinum as the central metal (Nature, 395,151(1998)), Eu(TTA)3phen which includes europium as the central metal(Jpn. J. Appl. Phys., 34, 1883(1995)) are known.

However, for forming a light emitting layer using the above well-knowntriplet light-emitting complexes, only the methods, such asvacuum-depositing method, are applicable, and it has been difficult toform a light emitting layer by coating method.

DISCLOSURE OF THE INVENTION

The object of the present invention is to provide a metal complex havingphosphorescence in visible region, which has more excellent lightemitting efficiency than the above-mentioned light-emitting materials.Moreover, the object of the present invention is to provide a new metalcomplex which has a triplet light-emitting complex structure in themolecule, and can be used for forming a light emitting layer by coatingmethod, and to provide a light-emitting device using said complex.

That is, the present invention provides a metal complex which has amonovalent group having a metal complex structure which shows lightemission from triplet excited state, and represented by the followingformula (1) or (2). Said complex can form an efficient light emittinglayer by coating method.

(In formula (1), A is a single bond or a divalent group derived fromconjugate system. R¹ and R² each independently represent a halogen atom,alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group,arylalkylamino group, arylalkyl silyl group, acyl group, acyloxy group,imino group, amide group, arylalkenyl group, arylalkynyl group, cyanogroup, or a monovalent heterocyclic group. R³represents alkyl group,aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or amonovalent heterocyclic group. a represents an integer of 0 to 3. brepresents an integer of 0 to 4. When a is two or more, a plurality ofR¹s may be the same or different. When b is two or more, a plurality ofR²s may be the same or different.)

(In formula (2), D is a single bond or a divalent group derived fromconjugate system. R⁴ and R⁵ each independently represent a halogen atom,alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group,arylalkyl amino group, arylalkyl silyl group, acyl group, acyloxy group,imino group,. amide group, arylalkenyl group, arylalkynyl group, cyanogroup, or a monovalent heterocyclic group. c and d each independentlyrepresent an integer of 0 to 4. When c is two or more, a plurality ofR⁴s may be the same or different. When d is two or more, a plurality ofR⁵ may be the same or different.)

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the metal complex structure showing lightemission from triplet excited state means a structure derived from atriplet light-emitting complex.

The triplet light-emitting complex which is a ground material of themetal complex structure showing light emission from triplet excitedstate will be explained.

The triplet light-emitting complex is usually a heavy metal complex, forexample, a complex which may generate phosphorescence emission from saidcomplex. Complexes in which fluorescence emission is observed inaddition to phosphorescence emission are also included.

The triplet light-emitting complexes are those having been used as a lowmolecular weight EL material. Such materials are disclosed, for example,in: Nature, (1998) 395, 151; Appl. Phys. Lett., (1999) 75(1), 4; Proc.SPIE—Int. Soc. Opt. Eng., (2001) 4105 ; (Organic Light-EmittingMaterials and Devices IV), 119; J. Am. Chem. Soc., (2001) 123, 4304;Appl. Phys. Lett., (1997) 71(18), 2596; Syn. Met., (1998) 94(1),103;Syn. Met., (1999) 99(2), 1361; and Adv. Mater., (1999), 11 (10),852.

The central metal of the metal complex structure showing light emissionfrom triplet excited state of the present invention is usually an atomhaving atomic number of 50 or more, spin-orbit interaction occurs in thecomplex, and intersystem crossing between a singlet state and a tripletstate can occur in the metal.

As the central metal, exemplified are rhenium, iridium, osmium,scandium, yttrium, platinum, gold; and lanthanoids such as europium,terbium, thulium, dysprosium, samarium, praseodymium, gadolinium, etc.Iridium, platinum, gold, and europium are preferable; iridium, platinum,and gold are especially preferable; and iridium is the most preferable.

The ligand of the triplet light-emitting complex is usually an organicligand, and the number of carbon atoms is usually about 3 to 60.

As the ligand of the triplet light-emitting complex, exemplified are8-quinolinol and derivatives thereof, benzoquinolinol and derivativesthereof, 2-phenyl-pyridine and derivatives thereof,2-phenyl-benzothiazole and derivatives thereof, 2-phenyl-benzoxazole andderivatives thereof, porphyrin derivatives thereof, etc.

As the triplet light-emitting complex, followings are exemplified.

Here, R each independently represent a group selected from a halogenatom, alkyl group, alkoxy group, alkylthio group, alkylamino group,alkyl silyl group, aryl group, aryloxy group, arylthio group, aryl aminogroup, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthiogroup, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxygroup, imino group, amide group, arylalkenyl group, arylalkynyl group,cyano group, monovalent heterocyclic group, a group represented by theabove formula (1), and a group represented by the above formula (2). Inorder to improve the solubility into a solvent, it is preferable thatone or more of Rs contain an alkyl chain having cyclic or long chain,and examples of R include a cyclopentyl group, cyclohexyl group, pentylgroup, hexyl group, octyl group, 2-ethylhexyl group, decyl group, and3,7-dimethyloctyl group. Two substituents may be connected to form aring. Furthermore, a part of carbon atoms in alkyl chain may be replacedby a group having a hetero atom, and examples of the hetero atom includean oxygen atom, a sulfur atom, a nitrogen atom, etc. Examples of thehalogen atom include fluorine, chlorine, bromine, and iodine.

The alkyl group may be any of linear, branched or cyclic, and may haveone or more substituents. The number of carbon atoms is usually fromabout 1 to 20, and specific examples thereof include methyl group, ethylgroup, propyl group, i-propyl group, butyl group, i-butyl group, t-butylgroup, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group,heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group,3,7-dimethyloctyl group, lauryl group, trifluoromethyl group,pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group,perfluorooctyl group, etc.; and pentyl group, hexyl group, octyl group,2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group arepreferable.

The alkoxy group may be any of linear, branched or cyclic, and may haveone or more substituents. The number of carbon atoms is usually fromabout 1 to 20, and specific examples thereof include methoxy group,ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxygroup, t-butoxy group, pentyloxy group, cyclopentyloxy group, hexyloxygroup, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyl octyloxygroup, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group,perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group,methoxymethyloxy group, 2-methoxyethyloxy group, etc.; and pentyloxygroup, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxygroup, and 3,7-dimethyloctyloxy group are preferable.

The alkylthio group may be any of linear, branched or cyclic, and mayhave one or more substituents. The number of carbon atoms is usuallyfrom about 1 to 20, and specific examples thereof include methylthiogroup, ethylthio group, propylthio group, i-propylthio group, butylthiogroup, i-butylthio group, t-butylthio group, pentylthio group,cyclopentylthio group, hexylthio group, cyclohexylthio group, heptylthiogroup, octylthio group, 2-ethylhexylthio group, nonylthio group,decylthio group, 3,7-dimethyloctylthio group, laurylthio group,trifluoromethylthio group, etc.; and pentylthio group, hexylthio group,octylthio group, 2-ethylhexylthio group, decylthio group, and3,7-dimethyloctylthio group are preferable.

The alkylamino group may be any of linear, branched or cyclic, and maybe monoalkylamino group or dialkylamino group. The number of carbonatoms is usually from about 1 to 40, and specific examples thereofinclude methylamino group, dimethyl amino group, ethylamino group,diethylamino group, propyl amino group, dipropylamino group,i-propylamino group, diisopropylamino group, butylamino group,i-butylamino group, t-butylamino group, pentylamino group,cyclopentylamino group, hexylamino group, cyclohexylamino group,heptylamino group, octylamino group, 2-ethylhexylamino group, nonylaminogroup, decylamino group, 3,7-dimethyloctylamino group, laurylaminogroup, cyclopentylamino group, dicyclopentylamino group, cyclohexylaminogroup, dicyclohexylamino group, pyrrolidyl group, piperidyl group,ditrifluoromethylamino group, etc.; and pentylamino group, hexylaminogroup, octylamino group, 2-ethylhexylamino group, decylamino group, and3,7-dimethyl octylamino group are preferable.

The alkylsilyl group may be any of linear, branched or cyclic, and thenumber of carbon atoms is usually from about 1 to 60. Specific examplesthereof include trimethylsilyl group, triethylsilyl group,tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilylgroup, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group,pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilylgroup, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group,nonyldimethylsilyl group, decyldimethylsilyl group,3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group etc.;and pentyldimethylsilyl group, hexyldimethyl silyl group,octyldimethylsilyl group, 2-ethylhexyl-dimethyl silyl group,decyldimethylsilyl group, and 3,7-dimethyloctyl dimethylsilyl group arepreferable.

The aryl group may have one or more substituents, and the number ofcarbon atoms is usually from about 6 to 60. Specific examples thereofinclude phenyl group, C₁-C₁₂ alkoxyphenyl group (C₁-C₁₂ represents thenumber of carbon atoms 1-12. Hereafter the same.), C₁-C₁₂ alkylphenylgroup, 1-naphtyl group, 2-naphtyl group, pentafluorophenyl group,pyridyl group, pyridazinyl group, pyrimidyl group, pyrazyl group,triazyl group, etc.; and C₁-C₁₂ alkoxyphenyl group, and C₁-C₁₂alkylphenyl group are preferable.

The aryloxy group may have one or more substituents on the aromaticring, and the number of carbon atoms is usually from about 6 to 60.Specific examples thereof include phenoxy group, C₁-C₁₂ alkoxyphenoxygroup, C₁-C₁₂ alkylphenoxy group, 1-naphtyloxy group, 2-naphtyloxygroup, pentafluorophenyloxy group, pyridyloxy group, pyridazinyloxygroup, pyrimidyloxy group, pyrazyloxy group, triazyloxy group, etc.; andC₁-C₁₂ alkoxyphenoxy group, and C₁-C₁₂ alkylphenoxy group arepreferable.

The arylthio group may have one or more substituents on the aromaticring, and the number of carbon atoms is usually from about 6 to 60.Specific examples thereof include phenylthio group, C₁-C₁₂alkoxyphenylthio group, C₁-C₁₂ alkyl phenylthio group, 1-naphthylthiogroup, 2-naphthylthio group, pentafluorophenylthio group, pyridylthiogroup, pyridazinylthio group, pyrimidylthio group, pyrazylthio group,triazylthio group, etc.; and C₁-C₁₂ alkoxyphenylthio group, and C₁-C₁₂alkylphenylthio group are preferable.

The arylamino group may have one or more substituents on the aromaticring, and the number of carbon atoms is usually from about 6 to 60.Specific examples thereof include phenylamino group, diphenylaminogroup, C₁-C₁₂ alkoxyphenylamino group, di(C₁-C₁₂ alkoxyphenyl)aminogroup, di(C₁-C₁₂ alkylphenyl)amino group, 1-naphtylamino group,2-naphtylamino group, pentafluorophenylamino group, pyridyl amino group,pyridazinylamino group, pyrimidylamino group, pyrazylamino group,triazylamino group, etc.; and C₁-C₁₂ alkylphenylamino group anddi(C₁-C₁₂ alkylphenyl)amino group are preferable.

The arylsilyl group may have one or more substituents on the aromaticring, and the number of carbon atoms is usually from about 6 to 60.Specific examples thereof include triphenyl silyl group,tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group,t-butyldiphenylsilyl group, dimethylphenylsilyl group, etc.

The arylalkyl group may have one or more substituents, and the number ofcarbon atoms is usually from about 7 to 60. Specific examples thereofinclude phenyl-C₁-C₁₂ alkyl group, C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkylgroup, C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkyl group, 1-naphtyl-C₁-C₁₂ alkylgroup, 2-naphtyl-C₁-C₁₂ alkyl group, etc.; and C₁-C₁₂alkoxyphenyl-C₁-C₁₂ alkyl group, and C₁-C₁₂ alkyl phenyl-C₁-C₁₂ alkylgroup are preferable.

The arylalkoxy group may have one or more substituents, and the numberof carbon atoms is usually from about 7 to 60. Specific examples thereofinclude phenyl-C₁-C₁₂ alkoxy group, C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkoxygroup, C₁-C₁₂ alkyl phenyl-C₁-C₁₂ alkoxy group, 1-naphtyl-C₁-C₁₂ alkoxygroup, 2-naphtyl-C₁-C₁₂ alkoxy group, etc.; and C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkoxy group, and C₁-C₁₂ alkyl phenyl-C₁-C₁₂ alkoxy groupare preferable.

The arylalkylthio group may have one or more substituents, and thenumber of carbon atoms is usually from about 7 to 60. Specific examplesthereof include phenyl-C₁-C₁₂ alkylthio group, C₁-C₁₂alkoxyphenyl-C₁-C₁₂ alkylthio group, C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkylthiogroup, 1-naphtyl-C₁-C₁₂ alkylthio group, 2-naphtyl-C₁-C₁₂ alkylthiogroup, etc.; and C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkylthio group, and C₁-C₁₂alkyl phenyl-C₁-C₁₂ alkylthio group are preferable.

The arylalkylamino group has usually about 7 to 60 carbon atoms.Specific examples thereof include phenyl-C₁-C₁₂ alkyl amino group,C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkylamino group, C₁-C₁₂ alkylphenyl-C₁-C₁₂alkylamino group, di(C₁-C₁₂ alkoxy phenyl-C₁-C₁₂ alkyl)amino group,di(C₁-C₁₂ alkyl phenyl-C₁-C₁₂ alkyl)amino group, 1-naphtyl-C₁-C₁₂alkylamino group, 2-naphtyl-C₁-C₁₂ alkylamino group, etc.; and C₁-C₁₂alkylphenyl-C₁-C₁₂ alkylamino group, and di(C₁-C₁₂ alkyl phenyl-C₁-C₁₂alkyl)amino group are preferable.

The arylalkylsilyl group has usually about 7 to 60 carbon atoms.Specific examples thereof include phenyl-C₁-C₁₂ alkyl silyl group,C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkylsilyl group, C₁-C₁₂ alkylphenyl-C₁-C₁₂alkylsilyl group, 1-naphtyl-C₁-C₁₂ alkylsilyl group, 2-naphtyl-C₁-C₁₂alkylsilyl group, phenyl-C₁-C₁₂ alkyldimethylsilyl group, etc.; andC₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkylsilyl group, and C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkylsilyl group are preferable.

The acyl group has usually about 2 to 20 carbon atoms. Specific examplesthereof include acetyl group, propionyl group, butyryl group, isobutyrylgroup, pivaloyl group, benzoyl group, trifluoroacetyl group,pentafluorobenzoyl group, etc.

The acyloxy group has usually about 2 to 20 carbon atoms. Specificexamples thereof include acetoxy group, propionyloxy group, butyryloxygroup, isobutyryloxy group, pivaloyloxy group, benzoyloxy group,trifluoroacetyloxy group, pentafluorobenzoyloxy group, etc.

The imino group has usually about 2 to 20 carbon atoms. Specificexamples thereof include the compounds represented by followingformulas.

The amide group has usually about 2 to 20 carbon atoms. Specificexamples thereof include formamide group, acetamide group, propioamidegroup, butyroamide group, benzamide group, trifluoroacetamide group,pentafluorobenzamide group, diformamide group, diacetoamide group,dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group, etc.; and imides such assuccinimide group and phthalic acid imide group, are also included.

The arylalkenyl group has usually about 7 to 60 carbon atoms Specificexamples thereof include phenyl-C₁-C₁₂ alkenyl group, C₁-C₁₂alkoxyphenyl-C₁-C₁₂ alkenyl group, C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkenylgroup, 1-naphtyl-C₁-C₁₂ alkenyl group, 2-naphtyl-C₁-C₁₂ alkenyl group,etc.; and C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkenyl group, and C₁-C₁₂alkylphenyl-C₁-C₁₂ alkenyl group are preferable.

The arylalkynyl group has usually about 7 to 60 carbon atoms. Specificexamples thereof include phenyl-C₁-C₁₂alkynyl group, C₁-C₁₂alkoxyphenyl-C₁-C₁₂ alkynyl group, C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkynylgroup, 1-naphtyl-C₁-C₁₂ alkynyl group, 2-naphtyl-C₁-C₁₂ alkynyl group,etc.; and C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkynyl group, and C₁-C₁₂alkylphenyl-C₁-C₁₂ alkynyl group are preferable.

The monovalent heterocyclic group means an atomic group in which ahydrogen atom is removed from a heterocyclic compound, and usually hasabout 4 to 60 carbon atoms. Specific examples thereof include thienylgroup, C₁-C₁₂ alkylthienyl group, pyroryl group, furyl group, pyridylgroup, C₁-C₁₂ alkylpyridyl group, etc.; and thienyl group, C₁-C₁₂alkylthienyl group, pyridyl group, and C₁-C₁₂ alkylpyridyl group, arepreferable. Furthermore, as for the aryl group and monovalentheterocyclic group in R, they may have one more or more substituents.

The metal complex of the present invention has a monovalent grouprepresented by the below formula (1) or (2). Thereby, light emittingefficiency can be improved.

In the formula, A is a single bond or a divalent group derived fromconjugate system. R¹ and R² each independently represent a halogen atom,alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group,arylalkylamino group, arylalkyl silyl group, acyl group, acyloxy group,imino group, amide group, arylalkenyl group, arylalkynyl group, cyanogroup, or a monovalent heterocyclic group. R³ represents alkyl group,aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or amonovalent heterocyclic group. a represents an integer of 0 to 3. brepresents an integer of 0 to 4. When a is two or more, a plurality ofR¹s may be the same or different, and mutually connected to form a ring.When b is two or more, a plurality of R²s may be the same or different,and mutually connected to form a ring.

In the formula, D is a single bond or a divalent group derived fromconjugate system. R⁴ and R⁵ each independently represent a halogen atom,alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group,arylalkyl amino group, arylalkyl silyl group, acyl group, acyloxy group,imino group, amide group, arylalkenyl group, arylalkynyl group, cyanogroup, or a monovalent heterocyclic group. c and d each independentlyrepresent an integer of 0 to 4. When c is two or more, a plurality ofR⁴s may be the same or different, and mutually connected to form a ring.When d is two or more, a plurality of R⁵ may be the same or different,and mutually connected to form a ring.

In R¹ to R⁵, the halogen atom, alkyl group, alkoxy group, alkylthiogroup, alkylamino group, alkylsilyl group, aryl group, aryloxy group,arylthio group, arylamino group, arylsilyl group, arylalkyl group,arylalkoxy group, arylalkylthio group, arylalkylamino group,arylalkylsilyl group, acyl group, acyloxy group, imino group, amidegroup, arylalkenyl group, arylalkynyl group, cyano group, and monovalentheterocyclic group, are the same as those of R exemplified above.

The divalent group derived from conjugate system in A or D is a grouphaving a resonance structure to which delocalized π electron pair,unpaired electron, or lone electron pair join, and exemplified arevinylene group, acetylene group, an arylene group, a divalentheterocyclic group, bonding units shown below, and two or morecombination thereof.

(In the formula, R′ represents alkyl group, aryl group, arylalkyl group,arylalkenyl group, arylalkynyl group, or a monovalent heterocyclicgroup.)

The arylene group has usually 6-60, preferably 6-20 carbon atoms, andexamples thereof include phenylene group (for example, followingformulas 1-3), naphthalenediyl group (following formulas 4-13),anthracenylene group (following formulas 14-19), biphenylene group(following formulas 20-25), triphenylene group (following formulas26-28), condensed-ring compound group (following formulas 29-38), etc.Here, the number of carbon atoms of substituent R is not counted as thenumber of carbon atoms of arylene group.

In the present invention, the divalent heterocyclic group means anatomic group in which two hydrogen atoms are removed from a heterocycliccompound, and the number of carbon atoms is usually 4-60, and preferably4-20. Here, the number of carbon atoms of substituent is not counted asthe number of carbon atoms of the divalent heterocyclic group.

The heterocyclic compound means an organic compound having a cyclicstructure in which at least one heteroatom such as oxygen, sulfur,nitrogen, phosphorus, boron, etc. is contained in the cyclic structureas the element other than carbon atoms.

Examples of the divalent heterocyclic group include followings.

Divalent heterocyclic groups containing nitrogen as a hetero atom;pyridine-diyl group (following formulas 39-44), diaza phenylene group(following formulas 45-48), quinolinediyl group (following formulas49-63), quinoxalinediyl group (following formulas 64-68), acridinediylgroup (following formulas 69-72), bipyridyldiyl group (followingformulas 73-75), phenanthrolinediyl group (following formulas 76-78),etc.

Groups having a fluorene structure containing silicon, nitrogen, sulfur,selenium, etc. as a hetero atom (following formulas 79-93). It ispreferable to have an aromatic amine monomer containing a nitrogen atom,such as carbazole of formulas 82-84 or triphenylaminediyl group, in viewof light emitting efficiency.

5 membered heterocyclic groups containing silicon, nitrogen, sulfur,selenium, etc. as a hetero atom: (following formulas 94-98).

Condensed 5 membered heterocyclic groups containing silicon, nitrogen,sulfur, selenium, etc. as a hetero atom: (following formulas 99-109),benzothiadiazole-4,7-diyl group, benzo oxadiazole-4,7-diyl group, etc.

5 membered heterocyclic groups containing silicon, nitrogen, sulfur,selenium, etc. as a hetero atom, which are connected at the a positionof the hetero atom to form a dimer or an oligomer (following formulas110-118); and

5 membered ring heterocyclic groups containing silicon, nitrogen,oxygen, sulfur, selenium, as a hetero atom is connected with a phenylgroup at the a position of the hetero atom (following formulas 112-118).

Here, R is the same group as those described above.

Concrete examples of A or D include following groups without beinglimited thereto.

The complex of the present invention is represented by the below formula(3), and is characterized by having phosphorescence in a visible region.

Here, the phosphorescence in a visible region means phosphorescencehaving emission wavelength of 380-800 nm.

M¹ is a metal which is an atom having an atomic number of 50 or more,and intersystem crossing between a singlet state and a triplet state canoccur in this complex by spin-orbit interaction. Examples of the atomrepresented by M¹ include: a rhenium atom, an osmium atom, an iridiumatom, a platinum atom, a gold atom, a lanthanum atom, a cerium atom, apraseodymium atom, a neodymium atom, a promethium atom, a samarium atom,an europium atom, a gadolinium atom, a terbium atom, a dysprosium atom,etc.; preferably a rhenium atom, an osmium atom, an iridium atom, aplatinum atom, a gold atom, a samarium atom, an europium atom, agadolinium atom, a terbium atom, and a dysprosium atom; and morepreferably, an iridium atom, a platinum atom, a gold atom, and aneuropium atom.

L² represents: a ligand which bonds to M¹ by one or more of nitrogenatom, oxygen atom, carbon atom, sulfur atom, or phosphorus atom; ahalogen atom; or a hydrogen atom.

Here, as the ligand which bonds to M¹ by one or more of nitrogen atom,oxygen atom, carbon atom, sulfur atom, or phosphorus atom, may bezero-valent, mono-valent, or multi-valent.

Examples thereof include: alkyl group, alkoxy group, acyloxy group,alkylthio group, alkylamino group, aryl group, aryloxy group, arylthiogroup, arylamino group, arylalkyl group, aryl alkoxy group,arylalkylthio group, arylalkylamino group, sulfonate group, cyano group,heterocyclic ligand, carbonyl compound, ether, amine, imine, phosphine,phosphite, and sulfide; and multi-dentate ligands derived fromcombinations thereof.

As the alkyl group, alkoxy group, alkylthio group, alkylamino group,aryl group, aryloxy group, arylthio group, arylamino group, arylalkylgroup, arylalkoxy group, arylalkylthio group, and arylalkylamino group,the groups described in the above R are exemplified.

Examples of the heterocyclic ligand include:

a pyridine ring, pyrrole ring, thiophene ring, oxazole, and furan ring;and monovalent ligands in which a hydrogen atom is removed from theseheterocyclic ring compounds.

Acyloxy group has about 2 to 20 carbon atoms, and specific examplesthereof include acetyloxy group, trifluoroacetyloxy group, propionyloxygroup, and benzoyloxy group. Examples of sulfonate group include benzenesulfonate group, p-toluene sulfonate group, methanesulfonate group,ethane sulfonate group, and trifluoromethane sulfonate group.

The carbonyl compound has a coordinate bond to M¹ through the oxygenatom, and examples thereof include: carbon monoxide; ketones such asacetone, and benzophenone; and diketones such as acetylacetone, andacenaphtoquinone.

The ether has a coordinate bond to M¹ through the oxygen atom, andexamples thereof include dimethylether, diethylether, tetrahydrofuran,1,2-dimethoxyethane, etc.

The amine has a coordinate bond to M¹ through the nitrogen atom, andexamples thereof include: monoamines such as tri methylamine,triethylamine, tributylamine, tribenzylamine, triphenylamine,dimethylphenyl amine, and methyldiphenyl amine; and diamines such as1,1,2,2-tetramethylethylene diamine, 1,1,2,2-tetraphenylethylenediamine,and 1,1,2,2-tetramethyl-o-phenylenediamine.

The imine has a coordinate bond to M¹ through the nitrogen atom, andexamples thereof include: monoimines such as benzylidene aniline,benzylidenebenzylamine, and benzylidene methylamine; and diimines suchas dibenzylidine ethylene diamine, dibenzylidine-o-phenylene diamine,and 2,3-bis(anilino)butane.

The phosphine has a coordinate bond to M¹ through the phosphorus atom,and examples thereof include triphenylphosphine, tri-o-tolylphosphine,tri-t-butylphosphine, tricyclohexyl phosphine,1,2-bis(diphenylphosphino)ethane, and 1,3-bis(diphenylphosphino)propane.

The phosphate has a coordinate bond to M¹ through the phosphorus atom,and examples thereof include trimethylphosphite, triethylphosphite,triphenylphosphite, and tribenzylphosphate.

The sulfide has a coordinate bond to M¹ through the sulfur atom, andexamples thereof include dimethylsulfide, diphenyl sulfide, andthioanisole.

Examples of the multi-dentate ligands derived from combinations thereofinclude:

groups derived from the combination of a heterocyclic ring and a benzenering such as phenylpyridine, 2-(paraphenylphenyl)pyridine,2-phenylbenzoxazole, 2-(paraphenylphenyl)benzoxazole,2-phenylbenzothiazole, 2-(paraphenylphenyl)benzothiazole, etc.;

groups derived from the combination of two or more heterocyclic ringssuch as 2-(4-thiophene-2-yl)pyridine, 2-(4-phenylthiophene-2-yl)pyridine, 2-(benzothiophene-2-yl)pyridine,2,3,7,8,12,13,17,18-octa ethyl-21H,23H-porphyrin, etc.; and acetonatessuch as acetylacetonate, dibenzomethylate, andthenoyltrifluoroacetonate.

l represents an integer of 1 to 3. m represents an integer of 0 to 3.When m is two or more, a plurality of L²s may be the same or different.l+m is an integer of 2 to 6.

L¹ in formula (3) represents a ligand represented by the followingformula (4) or formula (5).

(Here, Ar¹ represents a residue of a ligand which bonds to M¹ by one ormore of nitrogen atom, oxygen atom, carbon atom, sulfur atom, orphosphorus atom, and has covalent bonds to j pieces of As. j representsan integer of 1 to 3. In the formula, R¹ to R³, A, a, b, and j are thesame as those of the above formula (1)).

(Here, Ar² represents a residue of a ligand which bonds to M¹ by one ormore of nitrogen atom, oxygen atom, carbon atom, sulfur atom, orphosphorus atom, and has covalent bonds to k pieces of Ds. In theformula, R⁴, R⁵, D, c, d, and k are the same as those of the aboveformula (2)).

In respect of the stability of a compound, it is preferable that L¹ hasa coordinate bond to M¹ through at least one nitrogen atom or at leastone carbon atom, and it is more preferable that L¹ is a multi-dentateligand.

In view of light emitting efficiency, it is preferable that L¹ is aligand represented by the above formula (4).

It is also preferable that L¹ is a ligand represented by the aboveformula (5), and D is a ligand of divalent group derived from conjugatesystem.

It is more preferable that Ar¹ or Ar²is a monovalent ligand representedby the below formula (6) or (7).

(here, R⁶ to R¹³ each independently represent a hydrogen atom, halogenatom, alkyl group, alkoxy group, alkylthio group, alkylamino group,alkylsilyl group, aryl group, aryloxy group, arylthio group, arylaminogroup, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthiogroup, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxygroup, imino group, amide group, arylalkenyl group, arylalkynyl group,cyano group, monovalent heterocyclic group, or a group represented bythe above formula (1) or formula (2), and they may be connected to forma ring. At least one of R⁶ to R¹³ is one represented by the aboveformula (1) or formula (2).)

(In the formula, E¹ represents an oxygen atom or a sulfur atom.) R¹⁴ toR¹⁹ each independently represent a hydrogen atom, halogen atom, alkylgroup, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, aryl alkoxy group, arylalkylthiogroup, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxygroup, imino group, amide group, arylalkenyl group, arylalkynyl group,cyano group, monovalent heterocyclic group, or a group represented bythe above formula (1) or formula (2), and they may be connected to forma ring. At least one of R¹⁴ to R¹⁹ is one represented by the aboveformula (1) or formula (2).)

In respect to light emitting efficiency, it is preferable that M¹ is aniridium atom, platinum atom, gold atom, or europium atom.

Examples of L¹ include followings.

Here, R″ each independently represent a hydrogen atom, halogen atom,alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, aryl alkoxy group, arylalkylthiogroup, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxygroup, imino group, amide group, arylalkenyl group, arylalkynyl group,cyano group, monovalent heterocyclic group, and a group represented bythe above formula (1), or formula (2) Specific examples include thoserepresented in the above R. In each ligand, at least one R″ isrepresented by the above formula (1) or formula (2). R″s may beconnected mutually to form a ring. In order to improve the solubilityinto a solvent, it is preferable that at least one of the R″ has a longalkyl group.

Examples of L¹ represented by formula (4) include followings.

In the formula, R′ represents an alkyl group, aryl group, arylalkylgroup, arylalkenyl group, arylalkynyl group, or monovalent heterocyclicgroup.

Examples of L¹ represented by formula (5) include the followingstructures.

Specific examples of the complex represented by formula (3) is shownbelow.

The complexes represented by the above formula (3) can be manufactured,for example, by a condensation reaction of a complex represented by thebelow formula (17) with a carbazole derivative represented by the belowformula (18) or (19).

(Here, M¹, Ar¹, L², l, and m are the same as those of the above. x¹represents a halogen atom, sulfonate group, boric acid group, boricester group, sulfonium methyl group, phosphonium methyl group,phosphonate methyl group, monohalogenated methyl group, formyl group,cyano group, or vinyl group.)

(Here, A, R¹, R², R³, a, and b are the same as those of the above. x²represents a halogen atom, sulfonate group, boric acid group, boricester group, sulfonium methyl group, phosphonium methyl group,phosphonate methyl group, monohalogenated methyl group, formyl group,cyano group, or vinyl group.)

(Here, D, Ar³, R⁴, R⁵, c, d, e, and x² are the same as those of theabove.

As the halogen atom in x¹ and x², chlorine, bromine, and iodine areexemplified.

As the sulfonate group, benzene sulfonate group, p-toluene sulfonategroup, methane sulfonate group, ethane sulfonate group, andtrifluoromethane sulfonate group are exemplified.

As the boric ester group, groups represented by the below formulae areexemplified.

As the sulfonium methyl group, groups represented by the below formulaeare exemplified.—CH₂SMe₂X—CH₂SPh₂X

(X represents a halogen atom.)

As the phosphonium methyl group, a group represented by the belowformula is exemplified.—CH₂PPh₃X (X represents a halogen atom.)

As the phosphonate methyl group, a group represented by the belowformula is exemplified—CH₂P(═O)(OR′)₂

(R′ represents an alkyl group, aryl group, or arylalkyl group.)

As the monohalogenated methyl group, chloromethyl group, bromomethylgroup, and iodomethyl group are exemplified.

Examples of the condensation through a vinylene group include reactionssuch as: Wittig reaction of a compound having formyl group with acompound having phosphonium methyl group, or a compound having formylgroup and phosphonium methyl group;

Heck reaction of a compound having vinyl group with a compound havinghalogen atom; Knoevenagel reaction of a compound having formyl groupwith a compound having cyano group; and McMurry reaction of a compoundhaving formyl group, etc.

Examples of the formation of a single bond include Suzuki coupling, andGrignard coupling with using nickel catalyst.

The reactions can be carried out by solving in a organic solventaccording to the necessity, with using alkali or an appropriatecatalyst, at a temperature of from the melting point to the boilingpoint.

Known methods can be used described in: Organic Reactions, vol. 14, page270-490, John Wiley & Sons, Inc. (1965); Organic Syntheses, CollectiveVolume VI, page 407-411, John Wiley & Sons, Inc. (1988); Chem. Rev.,vol. 95, page 2457 (1995); J. Organomet. Chem., vol. 576, page 147(1999); J. Prakt. Chem., vol. 336, page 247 (1994); Makromol. Chem.,Macromol. Symp., vol. 12, page 229 (1987), etc.

They can be prepared also by a method of complex formation aftersynthesizing a ligand. As the synthetic method of the ligand, forexample, it can be manufactured by a condensation reaction of a compoundrepresented by the below formula (20) with a carbazole derivativerepresented by the above formula (18) or (19). Examples of thecondensation reaction are the same as those of the coupling reaction ofa complex represented by the above formula (17) with a carbazolederivative represented by the above formula (18) or (19).X¹—Ar¹—H  (20)

(Here, Ar¹ and x¹ are the same as those of the above.)

Examples of the method of complex formation from the above formula (20)include: in the case of an iridium complex, methods described in Inorg.Chem. 1991, 30, 1685 and Inorg. Chem. 2001, 40, 1704, etc.; in the caseof a platinum complex, methods described in Chem. Mater. 1999, 11, 3709;in the case of an europium complex, methods described in J. PolymerScience, Part A, 2000, 38, 3405; and in the case of a ruthenium complex,methods described in Polymer Bulletin, 1999, 43, 135 and J. Mater.Chem., 1999, 9, 2103.

It is preferable that the organic solvent used is subjected to adeoxygenation treatment sufficiently and the reaction is progressedunder an inert atmosphere, generally for suppressing a side reaction,though the treatment differs depending on the compound used and thereaction. Further, it is preferable to conduct a dehydration treatmentlikewise. However, this is not applicable in the case of a reaction in atwo-phase system with water, such as a Suzuki coupling reaction.

For the reaction, an alkali or suitable catalyst is added appropriately.These may be selected according to the reaction used. It is preferablethat the alkali or catalyst is soluble sufficiently in a solvent usedfor the reaction. As the method of mixing an alkali or catalyst, thereis exemplified a method of adding a solution of an alkali or catalystslowly while stirring under an inner atmosphere of argon and nitrogenand the like or a method of slowly adding the reaction solution to asolution of an alkali or catalyst, inversely.

Although the reaction temperature is not limited, it is usually about−100 to 350° C., and preferably from 0° C. to the boiling point ofsolvent. Although the reaction time is not limited, it is usually about30 minutes to 30 hours.

About the extraction and purification of the desired product from asolution of reaction mixture, it differs depending on the complexes, buttechniques of usual complex purification, such as recrystallization,sublimation, and chromatography, are used.

For example, 1N HCl aqueous solution which is a poor solvent to acomplex, is added to deposit the complex, and filtrated to obtain asolid, which is dissolved into an organic solvent, such asdichloromethane or chloroform. This solution is filtrated to removeinsoluble materials, concentrated again, and purified by silica gelcolumn chromatography (dichloromethane elution). The fraction solutionsof the desired product are collected, and for example, methanol (poorsolvent) is added in an appropriate amount, and concentrated to depositthe desired complex, which is filtrated, and dried, and the complex isobtained. The method of producing complex (3) of the present inventionis not limited to the above method.

For example, the complex of the present invention represented by thebelow formula (A) can be produced by the following synthetic route.

The polymeric light emitting substance of the present invention may havea metal complex structure showing light emission from triplet excitedstate in the main chain, in the side chain, or at the terminal of themain chain.

The polymeric light emitting substance having a metal complex structureshowing light emission from triplet excited state in the main chainmeans the case wherein an aromatic ring part or condensed ring partwhich coordinate to the complex showing light emission from tripletexcited state is contained in the main chain, or the case wherein ametal is contained in the main chain.

Specific examples of the metal complex structure showing light emissionfrom triplet excited state in the a main chain include the repeatingunit represented by the below formulas (8) and (9).

In the formula, M² is an atom having atomic number of 50 or more,spin-orbit interaction occurs in the complex, and thc intersystemcrossing between a singlet state and a triplet state can occur in themetal.

L³ represents a ligand represented by the below formula (12) or (13). L⁴represents: a ligand which bonds to M² with one or more of nitrogenatom, oxygen atom, carbon atom, sulfur atom, or phosphorus atom; ahalogen atom; or a hydrogen atom. e represents an integer of 1-3. frepresents an integer of 0-3. L⁵ is a ligand which bonds to M² with oneor more of nitrogen atom, oxygen atom, carbon atom, sulfur atom, orphosphorus atom, and has two bonds connected to two neighboringrepeating units with covalent bonding. When e is two or more, aplurality of L³ may be the same or different. When f is two or more, aplurality of L⁴ may be the same or different. Moreover, e+f is aninteger of 1-5.

(in the formula, Ar⁴ is a residue of the ligand which bonds to M² withone or more nitrogen atom, oxygen atom, carbon atom, sulfur atom, orphosphorus atom, and bonds to o pieces of As. o represents an integer of1-3. A, R¹-R³, a and b are respectively the same as those in the aboveformula (1).)

(In the formula, Ar⁵ is a residue of the ligand which bonds to M² withone or more nitrogen atom, oxygen atom, carbon atom, sulfur atom, orphosphorus atom, and has covalent bonds to p pieces of Ds. p representsan integer of 1-3. D, R⁴, R⁵, c, and d are respectively the same asthose in the above formula (2).)

(In the formula, M² , L³, and L⁴ are the same as above. L⁶ and L⁷ areeach independently, a ligand which bonds to M² with one or more nitrogenatom, oxygen atom, carbon atom, sulfur atom, or phosphorus atom, and hasa covalent bond to one neighboring repeating unit with one free bond,respectively. g represents an integer of 1-3 and h represents an integerof 0-3. When g or h is two or more, L³s or L⁴s may be the same ordifferent. Moreover, g+h is an integer of 1-4.)

As the metal complex structure showing light emission from tripletexcited state at the side chain, repeating units represented by thebelow formula (10) are specifically exemplified.

(In the formula, M², L³, L⁴, e, and f are the same as those in the aboveformula (8). Ar³ is a trivalent aromatic group or a trivalentheterocyclic group. L⁸ is a ligand which bonds to M² with one or morenitrogen atom, oxygen atom, carbon atom, sulfur atom, or phosphorusatom, and has a covalent bond to Ar³ with one free bond.)

As the metal complex structure showing light emission from tripletexcited state at the terminal of the main chain, repeating unitsrepresented by the below formula (11) are specifically exemplified.

(In the formula, M², L³, L⁴, e, and f are the same as those in the aboveformula (8). L⁹ is a ligand which bonds to M² with one or more nitrogenatom, oxygen atom, carbon atom, sulfur atom, or phosphorus atom, and hasa covalent bond at the polymer terminal with one free bond.)

Moreover, a metal complex structure showing light emission from tripletexcited state may be contained, and further a monovalent grouprepresented by the above formula (1) or (2) may be contained on arepeating unit other than said metal complex structure.

Examples of the atom represented by M² include rhenium atom, osmiumatom, iridium atom, platinum atom, gold atom, lanthanum atom, ceriumatom, praseodymium atom, neodymium atom, promethium atom, samarium atom,europium atom, gadolinium atom, terbium atom, and dysprosium atom.Rhenium atom, osmium atom, iridium atom, platinum atom, gold atom,samarium atom, europium atom, gadolinium atom, terbium atom, anddysprosium atom are preferable, and iridium atom, platinum atom, goldatom, and europium atom are more preferable.

Examples of the ligand which bonds to M² with one or more nitrogen atom,oxygen atom, carbon atom, sulfur atom, or phosphorus atom include analkyl group, alkoxy group, acyloxy group, alkylthio group, alkylaminogroup, aryl group, aryloxy group, arylthio group, arylamino group,arylalkyl group, aryl alkoxy group, arylalkylthio group, arylalkyl aminogroup, sulfonate group, cyano group, heterocyclic ligand, carbonylcompound, ether, amine, imine, phosphine, phosphite, and sulfide, andmulti-dentate ligand derived from combination thereof. Specifically, thecompounds described in L² are exemplified.

The trivalent heterocyclic group in the present invention means anatomic group in which three hydrogen atoms are removed from aheterocyclic compound, and usually has 4 to 60, and preferably 4 to 20carbon atoms. The number of carbon atoms of a substituent is not countedas the number of carbon atoms of the trivalent aromatic compound.

Specific examples thereof include groups described in A and D wherein ahydrogen atom is removed from the groups exemplified as a divalentheterocyclic group.

The polymeric compound of the present invention may have two or morekinds of repeating units represented by the above formulaa (8)-(10). Theamount of these repeating units is usually 0.01-50% by mole to the totalmoles of all repeating units, and preferably 0.1-10% by mole.

Examples of the metal complex structure showing light emission fromtriplet excited state in the main chain, include specifically thefollowing structures.

Moreover, examples of the case contained at the terminal of the mainchain, include the following structures.

The polymeric light emitting substance having a metal complex structureshowing light emission from triplet excited state in the side chainmeans the case wherein an aromatic ring part or condensed ring partwhich coordinate to the complex showing light emission from tripletexcited state is connected to the main chain through bonding. Here, thebond means a direct bond such as a direct bond and a double bond; a bondthrough an atom, such as oxygen atom, sulfur atom, and selenium atom; ora bond through a divalent-bond such as a methylene group, alkylenegroup, and arylene group, etc.

Among them, it is preferable that a metal complex structure showinglight emission from triplet excited state is contained in a side chainhaving conjugated bonding, and it is more preferable that an aromaticring contained in at least one ligand of said metal complex structureand an aromatic ring contained in the polymer main chain are connectedthrough a carbon-carbon single bond.

Specifically, following structures are exemplified. The free bond is abonding group to the main chain.

In the above formula, M is an atom having atomic number of 50 or more,

spin-orbit interaction occurs in the complex, and the intersystemcrossing between a singlet state and a triplet state can occur in themetal .

L is a ligand of M, and represents an alkyl group, alkoxy group,alkylthio group, alkylamino group, aryl group, aryloxy group, arylthiogroup, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthiogroup, arylalkylamino group, sulfonate group, heterocyclic group,acyloxy group, cyano group, heterocyclic ligand, carbonyl compound,ether, amine, imine, phosphine, phosphate, or sulfide, and may be amulti-dentate ligand derived from the combination thereof.

o represents an integer of 1-5. When o is two or more, Ls may bemutually the same, or different.

Examples of the atom represented by M include: rhenium atom, osmiumatom, iridium atom, platinum atom, gold atom, lanthanum atom, ceriumatom, praseodymium atom, neodymium atom, promethium atom, samarium atom,europium atom, gadolinium atom, terbium atom, dysprosium atom, etc.;preferably, rhenium atom, osmium atom, iridium atom, platinum atom, goldatom, samarium atom, europium atom, gadolinium atom, terbium atom, anddysprosium atom; and more preferably, iridium atom, platinum atom, goldatom, and europium atom.

The ligand represented by L may be zero-valent, mono-valent or more. Inthe group represented by L, examples of alkyl group, alkoxy group,alkylthio group, alkylamino group, aryl group, aryloxy group, arylthiogroup, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthiogroup, arylalkylamino group, heterocyclic group, acyloxy group, carbonylcompound, ether, amine, imine, phosphine, phosphite, and sulfide,include the compounds described in the above R².

Of the polymeric light-emitting substance of the present invention, itis preferable that the main chain is a conjugated type polymericlight-emitting substance. Here, the conjugated type polymericlight-emitting substance means a polymeric light-emitting substance inwhich delocalized π electron pair exist along with the main-chain of thepolymer, i.e., a polymeric light-emitting substance whose main chain isa conjugated polymer. As this delocalized electron, a unpaired electronor a lone electron pair may join to the resonance instead of a doublebond.

One embodiment of the present invention is a polymeric light-emittingsubstance having two or more kinds of metal complex structures showinglight emission from triplet excited state, i.e., a polymericlight-emitting substance having 2 or more kinds of metal complexstructures showing light emission from triplet excited state, on two ormore of the main chain, side chain, or the terminal. Metal complexstructures may have the same metal each other, and may have differentmetals. Moreover, metal complex structures may have mutually differentlight emission color. For example, exemplified is a case where both of ametal complex structure which emits green light and a metal complexstructure which emits red light are contained in one polymericlight-emitting substance. The case is preferable, since a light emissioncolor is controllable by designing to contain an appropriate amount ofthe metal complex structure.

As for the polymeric light-emitting substance of the present invention,it is preferable that the repeating unit represented by the belowformula (14) is contained.

(In the formula, Ar⁶ represents an arylene group or a divalentheterocyclic group. These groups may have a substituent. R²⁰ and R²¹each independently represent a hydrogen atom, alkyl group, aryl group,arylalkyl group, arylalkenyl group, arylalkynyl group, monovalentheterocyclic group, cyano group, and a group represented by the aboveformula (1) or formula (2). At least one of R²⁰, R²¹, or thesubstituents on Ar⁶, represents a group represented by the above formula(1) or (2). n is 0 or 1.)

As the alkyl group, aryl group, and monovalent heterocyclic grouprepresented by R²⁰ or R²¹, exemplified are the same as those of theabove R.

As the arylene group and divalent heterocyclic group represented by Ar⁶,exemplified are the same as those of the above A or D.

As for the polymeric light-emitting substance of the present invention,it is preferable that the repeating unit represented by the belowformula (21) is included in respect of light emitting efficiency.

(In the formula, Ar⁷ and Ar⁸ each independently represent an arylenegroup or a divalent heterocyclic group. R³⁶ represents alkyl group, arylgroup, monovalent heterocyclic group, a group represented by the aboveformula (1), a group represented by the above formula (2), a grouprepresented by the following formula (22), or a group represented by thefollowing formula (23). t is an integer of 1-4.)

(In the formula, Ar⁹ is an arylene group or a divalent heterocyclicgroup. R³⁷ is a hydrogen atom, alkyl group, aryl group, monovalentheterocyclic group, or a group represented by the below formula (23). Z¹represents —CR³⁸═CR³⁹— or —C≡C—. R³⁸ and R³⁹ each independentlyrepresent a hydrogen atom, alkyl group, aryl group, a monovalentheterocyclic group, a group represented by the above formula (1), agroup represented by the above formula (2), or cyano group. u is aninteger of 0-2.)

(In the formula, Ar¹⁰ and Ar¹¹ each independently represent an arylenegroup or a divalent heterocyclic group. R⁴⁰ represents an alkyl group,aryl group, a group represented by the above formula (1), a grouprepresented by the above formula (2), or a monovalent heterocyclicgroup. R⁴¹ represents a hydrogen atom, alkyl group, aryl group, ormonovalent heterocyclic group. v is an integer of 1-4.)

As the arylene group and divalent heterocyclic group in Ar⁷ to Ar¹¹,exemplified are the same as those of the above Ar¹.

As the alkyl group, aryl group and monovalent heterocyclic group in R³⁶to R⁴¹, exemplified are the same as those of the above R.

As the preferable example of the repeating unit represented by the aboveformula (21), exemplified are those represented by the followingformulae.

(In the formula, R is the same as that of the above.)

Furthermore, the end group of polymeric compound may also be protectedwith a stable group since if a polymerization active group remainsintact, there is a possibility of reduction in light emitting propertyand life-time when made into an device. Those having a conjugated bondcontinuing to a conjugated structure of the main chain are preferable,and there are exemplified structures connected to an aryl group orheterocyclic compound group via a carbon-carbon bond. Specifically, thefollowing structures are exemplified. (In the formula, R is the same asthat of the above.)

The polymer of the present invention may also be a random, block orgraft copolymer, or a polymer having an intermediate structure thereof,for example, a random copolymer having block property. From theviewpoint for obtaining a polymeric fluorescent substance having highfluorescent quantum yield, random copolymers having block property andblock or graft copolymers are more preferable than complete randomcopolymers. Further, a polymer having a branched main chain and morethan three terminals, and a dendrimer may also be included.

Furthermore, it is preferable that at least one of the ligands of themetal complex portion showing triplet light emission is a nitrogen atomor a carbon atom in view of the stability of a polymeric light emittingsubstance. Moreover, it is preferable that at least one of the ligandsis a multi-dentate ligand.

It is more preferable that at least one of the ligands is a monovalentligand represented by the below formula (15) or (16).

(In the formula, R²² to R²⁹ each independently represent a hydrogenatom, halogen atom, alkyl group, alkoxy group, alkylthio group,alkylamino group, alkylsilyl group, aryl group, aryloxy group, arylthiogroup, arylamino group, aryl silyl group, arylalkyl group, arylalkoxygroup, arylalkylthio group, arylalkylamino group, arylalkylsilyl group,acyl group, acyloxy group, imino group, amide group, arylalkenyl group,arylalkynyl group, cyano group, or monovalent heterocyclic group, andthey may be mutually connected to form a ring. At least one of R²² toR²⁹ is a free bond with a main chain or a side chain.)

(In the formula, E² represents an oxygen atom or a sulfur atom. R³⁰ toR³⁵ each independently represent a hydrogen atom, halogen atom, alkylgroup, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, aryl alkoxy group, arylalkylthiogroup, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxygroup, imino group, amide group, arylalkenyl group, arylalkynyl group,cyano group, or monovalent heterocyclic, and they may be mutuallyconnected to form a ring. At least one of R³⁰ to R³⁵ is a free bond witha main chain or a side chain.)

It is more preferable that the central metal of the metal complexportion showing light emission from triplet excited state is an iridiumatom, platinum atom, gold atom, or europium atom.

Next, the manufacture method of the polymeric light-emitting substanceof the present invention will be explained. The polymeric light-emittingsubstance of the present invention can be manufactured by a method ofcopolymerizing a monomer unit having a metal complex structure showinglight emission from a triplet state, with a monomer unit having acarbazole group represented by the above formula (1) or (2), or by amethod of polymerizing a monomer unit having a carbazole grouprepresented by the above formula (1) or (2) in the ligand, and having ametal complex structure showing light emission from triplet state.Moreover, the monomer unit having a metal complex structure showinglight emission from a triplet state, and the monomer unit having acarbazole group represented by the above formula (1) or (2), can be usedas two or more kinds thereof, and also can be used for thecopolymerization with a monomer unit containing neither the monomer unithaving a metal complex structure showing light emission from a tripletstate, nor the monomer unit having a carbazole group represented by theabove formula (1) or (2).

Specifically, it can be manufactured by carrying out condensationpolymerization of two or more monomers represented by the below formulas(24) and (25).

(In the formula, Ar⁶, R²⁰, R²¹, and n respectively represent the same asthose of the above formula (14). x³ and x⁴ each independently representa halogen atom, sulfonate group, boric-acid group, boric ester group,sulfonium methyl group, phosphonium methyl group, phosphonate methylgroup, monohalogenated methyl group, formyl group, cyano group, or vinylgroup.)

(In the formula, M² and L are the same as those of the above formula(8). Ar¹² represents a ligand which connects to M² with one or more of anitrogen atom, an oxygen atom, a carbon atom, a sulfur atom, or aphosphorus atom. X⁵ represents a halogen atom, sulfonate group,boric-acid group, boric ester group, sulfonium methyl group, phosphoniummethyl group, phosphonate methyl group, monohalogenated methyl group,formyl group, cyano group, or vinyl group. k represents an integer of1-3, and 1 represent an integer of 1-6, and m represents an integer of0-6.)

As the halogen atom, sulfonate group, boric-acid group, boric estergroup, sulfonium methyl group, phosphonium methyl group, phosphonatemethyl group, and monohalogenated-methyl group, in X³-X⁵, exemplifiedare the compounds of those described in the above X¹ and X².

As the method of reaction, an example of condensation reaction of theabove formula (17) with a carbazole derivative represented by (18) or(19) is specifically given.

The polymeric light-emitting substance of the present invention can bemanufactured also by a method of forming a complex, after manufacturinga polymeric compound having a structure of the ligand contained in themetal complex structure of the polymeric light-emitting substance in themain chain. In this case, it is preferable as the metal content can becontrolled.

Specifically, the following structures are exemplified.

As the method of forming a complex, the same methods of forming acomplex from the compound represented by the above formula (20) areexemplified.

It is preferable that the organic solvent used is subjected to adeoxygenation treatment sufficiently and the reaction is progressedunder an inert atmosphere, generally for suppressing a side reaction,though the treatment differs depending on compounds and reactions used.Further, it is preferable to conduct a dehydration treatment likewise.However, this is not applicable in the case of a reaction in a two-phasesystem with water, such as a Suzuki coupling reaction.

When these polymeric light-emitting substances of the present inventionare used for a light-emitting materials of a polymer LED, the puritythereof exerts an influence on light emitting property, therefore, it ispreferable that a monomer is purified by a method such as distillation,sublimation purification, re-crystallization and the like before beingpolymerized. Further, it is preferable to conduct a purificationtreatment such as re-precipitation purification, chromatographicseparation and the like after the polymerization.

Next, the polymer LED of the present invention will be explained. Thepolymer LED of the present invention comprises an light emitting layerbetween the electrodes consisting of an anode and a cathode, and thelight emitting layer contains the polymeric light-emitting substance ofthe present invention.

As the polymer LED of the present invention, exemplified are: a polymerLED having an electron transporting layer between a cathode and a lightemitting layer; a polymer LED having an hole transporting layer betweenan anode and a light emitting layer; and a polymer LED having anelectron transporting layer between an cathode and a light emittinglayer, and a hole transporting layer between an anode and a lightemitting layer.

Also exemplified are: a polymer LED having a layer containing aconductive polymer between at least one of the electrodes and a lightemitting layer adjacently to the electrode; and a polymer LED having abuffer layer having a mean thickness of 2 nm or less between at leastone of the electrodes and a light emitting layer adjacently to theelectrode.

For example, the following structures a) to d) are specificallyexemplified.

a) anode/light emitting layer/cathode

b) anode/hole transporting layer/light emitting layer/cathode

c) anode/light emitting layer/electron transporting layer/cathode

d) anode/hole transporting layer/light emitting layer/electrontransporting layer/cathode (wherein, “/” indicates adjacent laminationof layers. Hereinafter, the same).

Herein, the light emitting layer is a layer having function to emitalight, the hole transporting layer is a layer having function totransport a hole, and the electron transporting layer is a layer havingfunction to transport an electron. Herein, the electron transportinglayer and the hole transporting layer are generically called a chargetransporting layer.

The light emitting layer, hole transporting layer and electrontransporting layer also may be used each independently in two or morelayers.

Of charge transporting layers disposed adjacent to an electrode, thathaving function to improve charge injecting efficiency from theelectrode and having effect to decrease driving voltage of an device areparticularly called sometimes a charge injecting layer (hole injectinglayer, electron injecting layer) in general.

For enhancing adherence with an electrode and improving charge injectionfrom an electrode, the above-described charge injecting layer orinsulation layer having a thickness of 2 nm or less may also be providedadjacent to an electrode, and further, for enhancing adherence of theinterface, preventing mixing and the like, a thin buffer layer may alsobe inserted into the interface of a charge transporting layer and lightemitting layer.

The order and number of layers laminated and the thickness of each layercan be appropriately applied while considering light emitting efficiencyand life of the device.

In the present invention, as the polymer LED having a charge injectinglayer (electron injecting layer, hole injecting layer) provided, thereare listed a polymer LED having a charge injecting layer providedadjacent to a cathode and a polymer LED having a charge injecting layerprovided adjacent to an anode.

For example, the following structures e) to p) are specificallyexemplified.

e) anode/charge injecting layer/light emitting layer/cathode

f) anode/light emitting layer/charge injecting layer/cathode

g) anode/charge injecting layer/light emitting layer/charge injectinglayer/cathode

h) anode/charge injecting layer/hole transporting layer/light emittinglayer/cathode

i) anode/hole transporting layer/light emitting layer/charge injectinglayer/cathode

j) anode/charge injecting layer/hole transporting layer/light emittinglayer/charge injecting layer/cathode

k) anode/charge injecting layer/light emitting layer/electrontransporting layer/cathode

l) anode/light emitting layer/electron transporting layer/chargeinjecting layer/cathode

m) anode/charge injecting layer/light emitting layer/electrontransporting layer/charge injecting layer/cathode

n) anode/charge injecting layer/hole transporting layer/light emittinglayer/electron transporting layer/cathode

o) anode/hole transporting layer/light emitting layer/electrontransporting layer/charge injecting layer/cathode

p) anode/charge injecting layer/hole transporting layer/light emittinglayer/electron transporting layer/charge injecting layer/cathode

As the specific examples of the charge injecting layer, there areexemplified layers containing an conducting polymer, layers which aredisposed between an anode and a hole transporting layer and contain amaterial having an ionization potential between the ionization potentialof an anode material and the ionization potential of a hole transportingmaterial contained in the hole transporting layer, layers which aredisposed between a cathode and an electron transporting layer andcontain a material having an electron affinity between the electronaffinity of a cathode material and the electron affinity of an electrontransporting material contained in the electron transporting layer, andthe like.

When the above-described charge injecting layer is a layer containing anconducting polymer, the electric conductivity of the conducting polymeris preferably 10⁻⁵ S/cm or more and 10³ S/cm or less, and for decreasingthe leak current between light emitting pixels, more preferably 10⁻⁵S/cm or more and 10² S/cm or less, further preferably 10⁻⁵ S/cm or moreand 10¹ S/cm or less.

Usually, to provide an electric conductivity of the conducting polymerof 10⁻⁵ S/cm or more and 10³ S/cm or less, a suitable amount of ions aredoped into the conducting polymer.

Regarding the kind of an ion doped, an anion is used in a hole injectinglayer and a cation is used in an electron injecting layer. As examplesof the anion, a polystyrene sulfonate ion, alkylbenzene sulfonate ion,camphor sulfonate ion and the like are exemplified, and as examples ofthe cation, a lithium ion, sodium ion, potassium ion, tetrabutylammonium ion and the like are exemplified.

The thickness of the charge injecting layer is for example, from 1 nm to100 nm, preferably from 2 nm to 50 nm.

Materials used in the charge injecting layer may properly be selected inview of relation with the materials of electrode and adjacent layers,and there are exemplified conducting polymers such as polyaniline andderivatives thereof, polythiophene and derivatives thereof, polypyrroleand derivatives thereof, poly(phenylene vinylene) and derivativesthereof, poly(thienylene vinylene) and derivatives thereof,polyquinoline and derivatives thereof, polyquinoxaline and derivativesthereof, polymers containing aromatic amine structures in the main chainor the side chain, and the like, and metal phthalocyanine (copperphthalocyanine and the like), carbon and the like.

The insulation layer having a thickness of 2 nm or less has function tomake charge injection easy. As the material of the above-describedinsulation layer, metal fluoride, metal oxide, organic insulationmaterials and the like are listed. As the polymer LED having aninsulation layer having a thickness of 2 nm or less, there are listedpolymer LEDs having an insulation layer having a thickness of 2 nm orless provided adjacent to a cathode, and polymer LEDs having aninsulation layer having a thickness of 2 nm or less provided adjacent toan anode.

Specifically, there are listed the following structures q) to ab) forexample.

q) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/cathode

r) anode/light emitting layer/insulation layer having a thickness of 2nm or less/cathode

s) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/insulation layer having a thickness of 2 nm orless/cathode

t) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/cathode

u) anode/hole transporting layer/light emitting layer/insulation layerhaving a thickness of 2 nm or less/cathode

v) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/insulation layer having athickness of 2 nm or less/cathode

w) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/electron transporting layer/cathode

x) anode/light emitting layer/electron transporting layer/insulationlayer having a thickness of 2 nm or less/cathode

y) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/electron transporting layer/insulation layer having athickness of 2 nm or less/cathode

z) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/electron transportinglayer/cathode

aa) anode/hole transporting layer/light emitting layer/electrontransporting layer/insulation layer having a thickness of 2 nm orless/cathode

ab) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/electron transportinglayer/insulation layer having a thickness of 2 nm or less/cathode

In producing a polymer LED, when a film is formed from a solution byusing such polymeric fluorescent substance soluble in an organicsolvent, only required is removal of the solvent by drying after coatingof this solution, and even in the case of mixing of a chargetransporting material and a light emitting material, the same method canbe applied, causing an extreme advantage in production. As the filmforming method from a solution, there can be used coating methods suchas a spin coating method, casting method, micro gravure coating method,gravure coating method, bar coating method, roll coating method, wirebar coating method, dip coating method, spray coating method, screenprinting method, flexo printing method, offset printing method, inkjetprinting method and the like.

Regarding the thickness of the light emitting layer, the optimum valuediffers depending on material used, and may properly be selected so thatthe driving voltage and the light emitting efficiency become optimumvalues, and for example, it is from 1 nm to 1 μm, preferably from 2 nmto 500 nm, further preferably from 5 nm to 200 nm.

In the polymer LED of the present invention, light emitting materialsother than the above-described polymeric fluorescent substance can alsobe mixed in a light emitting layer. Further, in the polymer LED of thepresent invention, the light emitting layer containing light emittingmaterials other than the above-described polymeric fluorescent substancemay also be laminated with a light emitting layer containing theabove-described polymeric fluorescent substance.

As the light emitting material, known materials can be used. In acompound having lower molecular weight, there can be used, for example,naphthalene derivatives, anthracene or derivatives thereof, perylene orderivatives thereof; dyes such as polymethine dyes, xanthene dyes,coumarine dyes, cyanine dyes; metal complexes of 8-hydroxyquinoline orderivatives thereof, aromatic amine, tetraphenylcyclopentane orderivatives thereof, or tetraphenylbutadiene or derivatives thereof, andthe like.

Specifically, there can be used known compounds such as those describedin JP-A Nos. 57-51781, 59-195393 and the like, for example.

When the polymer LED of the present invention has a hole transportinglayer, as the hole transporting materials used, there are exemplifiedpolyvinylcarbazole or derivatives thereof, polysilane or derivativesthereof, polysiloxane derivatives having an aromatic amine in the sidechain or the main chain, pyrazoline derivatives, arylamine derivatives,stilbene derivatives, triphenyldiamine derivatives, polyaniline orderivatives thereof, polythiophene or derivatives thereof, polypyrroleor derivatives thereof, poly(p-phenylenevinylene) or derivativesthereof, poly(2,5-thienylenevinylene) or derivatives thereof, or thelike.

Specific examples of the hole transporting material include thosedescribed in JP-A Nos. 63-70257, 63-175860, 2-135359, 2-135361,2-209988, 3-37992 and 3-152184.

Among them, as the hole transporting materials used in the holetransporting layer, preferable are polymer hole transporting materialssuch as polyvinylcarbazole or derivatives thereof, polysilane orderivatives thereof, polysiloxane derivatives having an aromatic aminecompound group in the side chain or the main chain, polyaniline orderivatives thereof, polythiophene or derivatives thereof,poly(p-phenylenevinylene) or derivatives thereof,poly(2,5-thienylenevinylene) or derivatives thereof, or the like, andfurther preferable are polyvinylcarbazole or derivatives thereof,polysilane or derivatives thereof and polysiloxane derivatives having anaromatic amine compound group in the side chain or the main chain. Inthe case of a hole transporting material having lower molecular weight,it is preferably dispersed in a polymer binder for use.

Polyvinylcarbazole or derivatives thereof are obtained, for example, bycation polymerization or radical polymerization from a vinyl monomer.

As the polysilane or derivatives thereof, there are exemplifiedcompounds described in Chem. Rev., 89, 1359 (1989) and GB 2300196published specification, and the like. For synthesis, methods describedin them can be used, and a Kipping method can be suitably usedparticularly.

As the polysiloxane or derivatives thereof, those having the structureof the above-described hole transporting material having lower molecularweight in the side chain or main chain, since the siloxane skeletonstructure has poor hole transporting property. Particularly, there areexemplified those having an aromatic amine having hole transportingproperty in the side chain or main chain.

The method for forming a hole transporting layer is not restricted, andin the case of a hole transporting layer having lower molecular weight,a method in which the layer is formed from a mixed solution with apolymer binder is exemplified. In the case of a polymer holetransporting material, a method in which the layer is formed from asolution is exemplified.

The solvent used for the film forming from a solution is notparticularly restricted providing it can dissolve a hole transportingmaterial. As the solvent, there are exemplified chlorine solvents suchas chloroform, methylene chloride, dichloroethane and the like, ethersolvents such as tetrahydrofuran and the like, aromatic hydrocarbonsolvents such as toluene, xylene and the like, ketone solvents such asacetone, methyl ethyl ketone and the like, and ester solvents such asethyl acetate, butyl acetate, ethylcellosolve acetate and the like.

As the film forming method from a solution, there can be used coatingmethods such as a spin coating method, casting method, micro gravurecoating method, gravure coating method, bar coating method, roll coatingmethod, wire bar coating method, dip coating method, spray coatingmethod, screen printing method, flexo printing method, offset printingmethod, inkjet printing method and the like, from a solution.

The polymer binder mixed is preferably that does not disturb chargetransport extremely, and that does. not have strong absorption of avisible light is suitably used. As such polymer binder, polycarbonate,polyacrylate, poly(methyl acrylate), poly(methyl methacrylate),polystyrene, poly(vinyl chloride), polysiloxane and the like areexemplified.

Regarding the thickness of the hole transporting layer, the optimumvalue differs depending on material used, and may properly be selectedso that the driving voltage and the light emitting efficiency becomeoptimum values, and at least a thickness at which no pin hole isproduced is necessary, and too large thickness is not preferable sincethe driving voltage of the device increases. Therefore, the thickness ofthe hole transporting layer is, for example, from 1 nm to 1 μm,preferably from 2 nm to 500 nm, further preferably from 5 nm to 200 nm.

When the polymer LED of the present invention has an electrontransporting layer, known compounds are used as the electrontransporting materials, and there are exemplified oxadiazolederivatives, anthraquinonedimethane or derivatives thereof, benzoquinoneor derivatives thereof, naphthoquinone or derivatives thereof,anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane orderivatives thereof, fluorenone derivatives, diphenyldicyanoethylene orderivatives thereof, diphenoquinone derivatives, or metal complexes of8-hydroxyquinoline or derivatives thereof, polyquinoline and derivativesthereof, polyquinoxaline and derivatives thereof, polyfluorene orderivatives thereof, and the like.

Specifically, there are exemplified those described in JP-A Nos.63-70257, 63-175860, 2-135359, 2-135361, 2-209988, 3-37992 and 3-152184.

Among them, oxadiazole derivatives, benzoquinone or derivatives thereof,anthraquinone or derivatives thereof, or metal complexes of8-hydroxyquinoline or derivatives thereof, polyquinoline and derivativesthereof, polyquinoxaline and derivatives thereof, polyfluorene orderivatives thereof are preferable, and2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, benzoquinone,anthraquinone, tris(8-quinolinol)aluminum and polyquinoline are furtherpreferable.

The method for forming the electron transporting layer is notparticularly restricted, and in the case of an electron transportingmaterial having lower molecular weight, a vapor deposition method from apowder, or a method of film-forming from a solution or melted state isexemplified, and in the case of a polymer electron transportingmaterial, a method of film-forming from a solution or melted state isexemplified, respectively.

The solvent used in the film-forming from a solution is not particularlyrestricted provided it can dissolve electron transporting materialsand/or polymer binders. As the solvent, there are exemplified chlorinesolvents such as chloroform, methylene chloride, dichloroethane and thelike, ether solvents such as tetrahydrofuran and the like, aromatichydrocarbon solvents such as toluene, xylene and the like, ketonesolvents such as acetone, methyl ethyl ketone and the like, and estersolvents such as ethyl acetate, butyl acetate, ethylcellosolve acetateand the like.

As the film-forming method from a solution or melted state, there can beused coating methods such as a spin coating method, casting method,micro gravure coating method, gravure coating method, bar coatingmethod, roll coating method, wire bar coating method, dip coatingmethod, spray coating method, screen printing method, flexo printingmethod, offset printing method, inkjet printing method and the like.

The polymer binder to be mixed is preferably that which does notextremely disturb a charge transport property, and that does not havestrong absorption of a visible light is suitably used. As such polymerbinder, poly(N-vinylcarbazole), polyaniline or derivatives thereof,polythiophene or derivatives thereof, poly(p-phenylene vinylene) orderivatives thereof, poly(2,5-thienylene vinylene) or derivativesthereof, polycarbonate, polyacrylate, poly(methyl acrylate), poly(methylmethacrylate), polystyrene, poly(vinyl chloride), polysiloxane and thelike are exemplified.

Regarding the thickness of the electron transporting layer, the optimumvalue differs depending on material used, and may properly be selectedso that the driving voltage and the light emitting efficiency becomeoptimum values, and at least a thickness at which no pin hole isproduced is necessary, and too large thickness is not preferable sincethe driving voltage of the device increases. Therefore, the thickness ofthe electron transporting layer is, for example, from 1 nm to 1 μm,preferably from 2 nm to 500 nm, further preferably from 5 nm to 200 nm.

The substrate forming the polymer LED of the present invention maypreferably be that does not change in forming an electrode and layers oforganic materials, and there are exemplified glass, plastics, polymerfilm, silicon substrates and the like. In the case of a opaquesubstrate, it is preferable that the opposite electrode is transparentor semitransparent.

At least one of the electrodes consisting of an anode and a cathode, istransparent or semitransparent. It is preferable that the anode istransparent or semitransparent.

As the material of this anode, electron conductive metal oxide films,semitransparent metal thin films and the like are used. Specifically,there are used indium oxide, zinc oxide, tin oxide, and films (NESA andthe like) fabricated by using an electron conductive glass composed ofindium/tin/oxide (ITO), indium/zinc/oxide and the like, which are metaloxide complexes, and gold, platinum, silver, copper and the like areused, and among them, ITO, indium/zinc/oxide, tin oxide are preferable.As the fabricating method, a vacuum vapor deposition method, sputteringmethod, ion plating method, plating method and the like are used. As theanode, there may also be used organic transparent conducting films suchas polyaniline or derivatives thereof, polythiophene or derivativesthereof and the like.

The thickness of the anode can be appropriately selected whileconsidering transmission of a light and electric conductivity, and forexample, from 10 nm to 10 μm, preferably from 20 nm to 1 μm, furtherpreferably from 50 nm to 500 nm.

Further, for easy charge injection, there may be provided on the anode alayer comprising a phthalocyanine derivative conducting polymers, carbonand the like, or a layer having an average film thickness of 2 nm orless comprising a metal oxide, metal fluoride, organic insulatingmaterial and the like.

As the material of a cathode used in the polymer LED of the presentinvention, that having lower work function is preferable. For example,there are used metals such as lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium, barium, aluminum,scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium,terbium, ytterbium and the like, or alloys comprising two of more ofthem, or alloys comprising one or more of them with one or more of gold,silver, platinum, copper, manganese, titanium, cobalt, nickel, tungstenand tin, graphite or graphite intercalation compounds and the like.Examples of alloys include a magnesium-silver alloy, magnesium-indiumalloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminumalloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminumalloy and the like. The cathode may be formed into a laminated structureof two or more layers.

The thickness of the cathode can be appropriately selected whileconsidering transmission of a light and electric conductivity, and forexample, from 10 nm to 10 μm, preferably from 20 nm to 1 μm, furtherpreferably from 50 nm to 500 nm.

As the method for fabricating a cathode, there are used a vacuum vapordeposition method, sputtering method, lamination method in which a metalthin film is adhered under heat and pressure, and the like. Further,there may also be provided, between a cathode and an organic layer, alayer comprising an conducting polymer, or a layer having an averagefilm thickness of 2 nm or less comprising a metal oxide, metal fluoride,organic insulation material and the like, and after fabrication of thecathode, a protective layer may also be provided which protects thepolymer LED. For stable use of the polymer LED for a long period oftime, it is preferable to provide a protective layer and/or protectivecover for protection of the device in order to prevent it from outsidedamage.

As the protective layer, there can be used a polymeric compound, metaloxide, metal fluoride, metal borate and the like. As the protectivecover, there can be used a glass plate, a plastic plate the surface ofwhich has been subjected to lower-water-permeation treatment, and thelike, and there is suitably used a method in which the cover is pastedwith an device substrate by a thermosetting resin or light-curing resinfor sealing. If space is maintained using a spacer, it is easy toprevent an device from being injured. If an inner gas such as nitrogenand argon is sealed in this space, it is possible to prevent oxidationof a cathode, and further, by placing a desiccant such as barium oxideand the like in the above-described space, it is easy to suppress thedamage of an device by moisture adhered in the production process. Amongthem, any one means or more are preferably adopted.

The polymer LED of the present invention can be used for a flat lightsource, a segment display, a dot matrix display, and a liquid crystaldisplay as a back light, etc.

For obtaining light emission in plane form using the polymer LED of thepresent invention, an anode and a cathode in the plane form may properlybe placed so that they are laminated each other. Further, for obtaininglight emission in pattern form, there is a method in which a mask with awindow in pattern form is placed on the above-described plane lightemitting device, a method in which an organic layer in non-lightemission part is formed to obtain extremely large thickness providingsubstantial non-light emission, and a method in which any one of ananode or a cathode, or both of them are formed in the pattern. Byforming a pattern by any of these methods and by placing some electrodesso that independent on/off is possible, there is obtained a displaydevice of segment type which can display digits, letters, simple marksand the like. Further, for forming a dot matrix device, it may beadvantageous that anodes and cathodes are made in the form of stripesand placed so that they cross at right angles. By a method in which aplurality of kinds of polymeric compounds emitting different colors oflights are placed separately or a method in which a color filter orluminescence converting filter is used, area color displays and multicolor displays are obtained. A dot matrix display can be driven bypassive driving, or by active driving combined with TFT and the like.These display devices can be used as a display of a computer,television, portable terminal, portable telephone, car navigation, viewfinder of a video camera, and the like.

Further, the above-described light emitting device in plane form is athin self-light-emitting one, and can be suitably used as a flat lightsource for back-light of a liquid crystal display, or as a flat lightsource for illumination. Further, if a flexible plate is used, it canalso be used as a curved light source or a display.

The polymeric light-emitting substance of the present invention hastriplet light-emitting complex structure in a molecule, and can form alight emitting layer by industrially simple application methods, such asa spin coat method, an ink-jet method, and a printing method. Moreover,the polymeric light-emitting substance of the present invention containstriplet light-emitting complex, and can show high light emittingefficiency. Therefore, the polymeric light-emitting substance of thepresent invention can be used preferably for light-emitting materials ofpolymer LED etc.

Hereafter, in order to explain the present invention in detail withshowing examples, but the present invention is not limited to these.

Here, about the number average molecular weight and the weight averagemolecular weight, the polystyrene reduced number average molecularweight and the weight average molecular weight were obtained by gelpermeation chromatography (GPC), using chloroform as a solvent.

<Synthesis of Monomer A-1>

1.55 g of phosphonate obtained by reacting1,4-dibromo-2,5-bis(bromomethyl)-benzene and phosphoric-acid triethyl,and 1.79 g of N-ethyl-3-carbazole carboxy aldehyde were dissolved in 30g of tetrahydrofuran (dehydrated). After adding a solution in which 0.9g of potassium-t-butoxide was dissolved beforehand in 10 g oftetrahydrofuran (dehydrated) dropwise into this solution at roomtemperature, it was succeedingly reacted at room temperature for 5hours.

After the reaction, this solution was neutralized with adding aceticacid, then methanol was added to this solution and resultingprecipitation was collected by filtration. The collected precipitationwas washed with ethanol, and dried under reduced-pressure and 1.5 g of acrude product was obtained. Next, it was re-crystallized from chloroformand purified monomer A was obtained.

¹H-NMR (200 MHz, CDCl₃) δ 8.24 (2H, brs), 8.14 (2H, d), 7.93 (2H, s),7.71 (2H, d), 7.52 (12H, m), 4.37 (4H, q), 1.45 (6H, t)

<Synthesis of Monomer A-2>Synthesis of 2-(bromophenyl)pyridine

3 g (19.3 mmol) of 2-phenyl pyridine and 40 mg (0.716 mmol) of ironpowder were mixed and stirred. It was cooled to 0° C. and 4.0 g (25mmol) of bromine was added dropwise with stirring, and watching heatgeneration, and it was raised to 90° C., and stirred for 10 hours. Afterthe reaction, this reaction mixture was dissolved in chloroform toproduce a solution, which was washed with 5% sodium thiosulfate aqueoussolution. The chloroform solution was dried with sodium sulfate, andthen concentrated. The residue was purified by silica gel columnchromatography, and the desired 2-(bromophenyl)pyridine was obtained.

The amount was 1.6 g (6.83 mmol), and the yield was 35.4%. By LC-MS, M+was 234.0.

Synthesis of tris(2-(bromophenyl)pyridine)iridium (III)

50 mg (0.1021 mmol) of trisacetylacetonate iridium (III) complex, 95.6mg (0.4084 mmol) of 2-bromophenyl pyridine, and 20 ml of glycol werecharged into a 50 ml eggplant type flask, and refluxed for 10 hours. 100ml of 1 N hydrogen chloride aqueous solution was added to this reactionsolution, and stirred for 30 minutes. The deposited solid was filtrated,and dissolved again in a small amount of methylene chloride to produce asolution. This solution was filtrated with silica gel columnchromatography, and the residual metal decomposition material originatedfrom the iridium complex was removed. Then, obtained solution wasconcentrated partway, and the yellow solid deposited by addition ofmethanol was filtrated and collected.

The desired product of tris(2-(bromophenyl)pyridine)iridium (III) 10.12mg (0.0113 mmol) was obtained. The yield was 11.1%. By FD-MS, M+ was893.

Synthesis of bis 2-(phenyl)pyridine)mono(2-(bromophenyl)pyridine)iridium(III) (Monomer A-2)

0.642 g (1.31 mmol) of trisacetylacetonate iridium (III) complex, 0.41 g(1.75 mmol) of 2-(bromophenyl)pyridine, 0.54 g (3.5 mmol) of2-(phenyl)pyridine, and 50 ml of glycol was supplied to were chargedinto a 100 ml eggplant type flask, and refluxed for 10 hours. 100 ml of1 N hydrogen chloride aqueous solution was added to this reactionsolution, and stirred for 30 minutes. The deposited solid was filtrated,and dissolved again in a small amount of methylene chloride to produce asolution. This solution was filtrated with silica gel columnchromatography, and the residual metal decomposition material originatedfrom the iridium complex was removed. Then, obtained solution wasconcentrated partway, and the yellow solid deposited by addition ofmethanol was filtrated and collected.

A mixture of bis(2-(phenyl)pyridine)mono(2-(bromophenyl)pyridine)iridium (III) as the main component wasobtained, 0.13 g (0.177 mmol equivalent). The yield was about 13.5%. ByFD-MS, M+ of the main component was 733. The mixture is a mixture of atris(2-(bromophenyl)pyridine)iridium (III) complex (complex 4),mono(2-(phenyl)pyridine) bis(2-(bromophenyl)pyridine)iridium (III)complex (complex 3), bis(2-(phenyl)pyridine)mono (2-(bromophenyl)pyridine)iridium (III) complex (complex 2), andtris(2-(phenyl)pyridine) iridium (III) complex (complex 1). Each ratiosby FD-MS, are represented in below Table 1. TABLE 1 Composition ofmonomer A-2 (mixture) FD-MS of complex Composition Peak ratio ratio (%)Note Complex 1 31 12.2 React to the end of the Complex 2 86 33.7molecule which is Complex 3 100 39.2 discharged without Complex 4 3814.9 reaction<Synthesis of Polymer A>

0.40 g (0.73 mmol) of 9,9-dioctyl-2,7-dibromo fluorene, 0.044 g (0.065mmol) of monomer A-1, 0.012 g (0.016 mmol) of monomer A-2, and 0.30 g(1.9 mmol) of 2,2′-bipyridyl were charged into a reaction vessel, andthen the inside of the reaction system was replaced with nitrogen gas.Into this, 20 ml of tetrahydrofuran (dehydrated solvent) which wasdeaerated with argon gas bubbling beforehand was added.

Next, 0.54 g (1.9 mmol) of bis(1,5-cyclooctadiene) nickel(0) was addedto this mixed solution, and it was reacted at 60° C. for 3 hours. Thereaction was conducted in nitrogen-gas atmosphere. After the reaction,this solution was cooled, and poured into a mixed solution of 25%aqueous ammonia 10 ml/methanol 120 ml/ion-exchanged water 50 ml, andstirred for about 1 hour. Next, the resulting precipitation wascollected by filtration. This precipitation was washed with ethanol, andthen dried under reduced-pressure for 2 hours. Next, this precipitationis dissolved in toluene 30 mL, 1N hydrogen chloride 30 mL is added toit, and stirred for 1 hour, and the aqueous layer was removed. 4%aqueous ammonia 30 mL was added to the organic layer, and the aqueouslayer was removed after stirring for 1 hour. The organic layer was addeddropwise into methanol 150 mL, and stirred for 1 hour, and the depositedprecipite was filtrated and dried under reduced-pressure for 2 hours,and then it was dissolved in toluene 30 mL. Then, it was purified bypassing through alumina column (alumina 20 g ), the collected toluenesolution was added to methanol 150 mL and stirred for 1 hour, thedeposited precipitate was filtrated and dried under reduced-pressure for2 hours. The yield of obtained copolymer was 0.14 g.

The polystyrene reduced number average molecular weight of the copolymerwas 9.2×10⁴, and the polystyrene reduced weight average molecular weightwas 3.9×10⁵.

<Synthesis of Complex B>

(Synthesis of 1-bromo-3-trifluoromethyl sulfonyloxy benzene)

12.1 g of 3-bromophenol, 12.8 g of 4-dimethylpyridine, and 50 ml ofmethylenechloride were charged into a four-necked flask under argonatmosphere. It was cooled with an ice bath, and 30 ml of methylenechloride solution of trifluoromethanesulfonic acid anhydride 24.7 g wasadded dropwise with ice bath cooling, for about 1 hour. The temperaturewas raised to room temperature by being left as it was, it was reactedat room temperature for 5 hours. The reaction mass was charged to silicagel and developed with toluene. The filtrate was concentrated and 20.4 gof a mixture containing 1-bromo-3-trifluoromethyl sulfonyloxy benzenewas obtained.

(Synthesis of 1-bromo-3-(2-thienyl)benzene)

2.2 g of lithium bromide was charged into a four-necked flask underargon atmosphere, and dried with heating under reduced pressure.Subsequently, under argon atmosphere, diethyl ether 10 ml was charged.Furthermore, 9.9 g of a mixture containing 1-bromo-3-trifluoromethylsulfonyloxybenzene and 0.72 g of[1,2-bis(diphenylphosphino)ethane]palladium (II) dichloride werecharged, and it was cooled with an ice bath. 45 ml diethyl ethersolution of 2-thienyl magnesium bromide (37.5 mmol) prepared by ordinarymethod, was added dropwise for about 10 minutes with ice bath cooling,and it was reacted for 6 hours.

The reaction mass was charged to silica gel and developed withchloroform. The filtrate was concentrated and a reaction mixture wasobtained. It was purified with silica gel column (eluent:cyclohexane/toluene=40/1), and 1.96 g of a mixture containing1-bromo-3-(2-thienyl)benzene was obtained.

(Synthesis of N-3-(2-thienyl)phenylcarbazole)

Under argon atmosphere, 1.0 g of carbazole, 1.75 g of a mixturecontaining 1-bromo-3-(2-thienyl)-benzene, 0.08 g oftris(dibenzylidineacetone)dipalladium(0), 0.86 g of sodiumtert-butoxide, and 5 ml of toluene and 0.06 g oftri(tert-butyl)phosphine were charged, and the temperature was raised to100° C. It was reacted at 100° C. for 9 hours. 0.04 g oftris(dibenzylidineacetone)dipalladium(0) and 0.03 g oftri(tert-butyl)phosphine were added, and further reacted at 100° C. for8 hours. Toluene 100 ml was added to the reaction mass, and washed andpartitioned by 30 ml of ion-exchanged water 2 times. The organic layerwas dried with anhydrous sodium sulfate, then filtrated andconcentrated, and a reaction mixture was obtained. It was purified withsilica gel column (eluent: cyclohexane/toluene=6/1), and 1.61 g ofN-3-(2-thienyl)phenylcarbazole was obtained.

LC/MS: APCI method [M+H]+=326

(Synthesis of Ligand B)

Under argon atmosphere, N-3-(2-thienyl)phenylcarbazole (2.5 mmol, 0.81g) and diethyl ether (5 ml) were charged into a four-necked flask. Itwas cooled with methanol/ice and n-butyl lithium (1.6M hexane solution)(2.3 ml) was added dropwise for about 5 minutes.

The temperature was raised to room temperature by being left as it was,and stirred for 10 minutes, then diethylether solution (0.5 ml) of2-fluoropyridine (2.5 mmol, 0.24 g) was added dropwise for about 5minutes. Then, the reaction was carried out with refluxing for 2 hours.After it was cooled to room temperature by being left as it was, 200 mlof toluene and 50 ml of ion-exchanged water were added and partitioned.The organic layer was dried with anhydrous sodium sulfate, filtrated andconcentrated, and a reaction mixture was obtained. It was purified withsilica gel column (eluent: cyclohexane/toluene=6/1), and 0.16 g ofligand B was obtained.

¹H-NMR (300 MHz, CDCl₃) d 8.58 (1H, d), 8.16 (2H, d), 7.89 (1H, brs),7.76 (1H, d), 7.70 to 7.14 (13H, m)

(Synthesis of Complex B)

57.3 mg of ligand B synthesized above, 17.4 mg of iridium (III)acetylacetonate, 10 ml of glycerol were charged, and replaced withargon. The temperature was raised to 200° C. for 1 hour, and was keptwarm for 8 hours. After standing to cool to room temperature, it wasadded into 1N hydrogen chloride aqueous solution (30 ml), and thedeposit was filtrated. The deposit was dissolved in a small amount ofmethylene chloride, and filtrated with silica gel column (eluent:methylene chloride). Obtained solution was concentrated and 13.7 mg oflight orange crystal was obtained. By FD/MS measurement, molecule ionpeak of complex B was detected.

FD/MS: 1397[M+]

<Synthesis of Complex C>(N-ethyl-3-bromocarbazole)

5.00 g of N-ethylcarbazole was dissolved in 130 ml of dehydrated DMF ina flask whose atmosphere was replaced with argon. This solution wascooled to 0° C., 4.60 g of N-bromosuccinimide was charged as 5 dividedfractions for 3 hours. After raising the temperature to room temperatureand stirring for 12 hours, the reaction liquid was thrown into icedwater and filtrated. The residue was washed with water and methanol, anddried under reduced-pressure to give 6.28 g crude product. It waspurified with silica gel column chromatography (eluent: cyclohexanecontaining 0.1% triethylamine), and 5.68 g of N-ethyl-3-bromo carbazolewas obtained.

¹H-NMR (300 MHz, CDCl₃) d 8.17 (1H, brs), 8.01 (1H, dd), 7.50 (1H, dd),7.46 (1H, d), 7.35 (1H, d), 7.24 to 7.17 (2H, m), 4.26 (2H, q), 1.39(3H, t)

MS (APCI, psitive)

m/z: 274, 276 [M+H]+

(N-ethyl-3-(3-trifluoromethanesulfonyloxyphenyl)carbazole)

1.00 g of N-ethyl-3-bromocarbazole was dissolved in 3.2 ml of dehydratedether in a Schrenck tube which was flame-dried and argon gas-replaced.This solution was cooled to −78° C., and 2.4 ml of n-butyl lithium(2.64M hexane solution) was added dropwise. After raising thetemperature to 0° C. and stirring for 1 hour, it was cooled again to−78° C., an ether solution of magnesium bromide prepared from magnesium0.4 g and 1,2-dibromoethane 0.8 g was added dropwise. After raising thetemperature to room temperature and stirring for 12 hours, this reactionsolution was added dropwise into a solution which was prepared bysuspending lithium bromide 0.28 g, 3-trifluoromethanesulfoxybromobenzene 0.82 g, anddichloro[1,3-bis(diphenylphosphino)propane]palladium(II) 0.09 g indehydrated diethylether 2 ml, and cooled at 0° C. After stirring for 7hours, 20 ml water was added dropwise and partitioned. The aqueous phasewas extracted twice with 40 ml toluene, and the combined aqueous phasewas washed with water and saturated NaCl aqueous solution, thenconcentrated, and 1.61 g of crude product was obtained. It was purifiedwith silica gel column chromatography (eluent,hexane:ethyl-acetate=25:1), 0.33 g of N-ethyl-3-(3-bromophenyl)carbazolewas obtained.

¹H-NMR (CDCl₃, 300 MHz) d 8.28 (1H, brs), 8.17 (1H, dd), 7.86 (1H, brs),7.68 to 7.61 (2H, m), 7.52 to 7.16 (6H, m), 4.39 (2H, q), 1.45 (3H, t)

MS (APCI, psitive)

m/z: 350, 352 [M+H]+

(Synthesis of Ligand C)

0.30 g of N-ethyl-3-(3-bromophenyl)carbazole was dissolved in 0.9 mldehydrated diethylether in a Schrenck tube which was flame-dried andargon gas-replaced, and it was cooled to −78° C.

After adding dropwise 0.4 ml (2.64M hexane solution) of n-butyl lithiuminto this solution, the temperature was raised to −10° C. and stirredfor 1 hour, and cooled to −78° C. again. To this solution, a solutionprepared by dissolving 0.08 g of 2-fluoropyridine in 0.9 ml ofdehydrated diethylether was added dropwise. The temperature was raisedgradually to room temperature, and it was stirred for 12 hours, thenpartitioned with adding 5 ml of water. The aqueous phase was extracted 3times with 5 ml toluene, and the combined organic phase was concentratedto give 0.39 g crude product.

MS (APCI, psitive) m/z: 349[M+H]+

(Synthesis of Complex C)

Complex C can be prepared by using ligand C instead of thesis of theabove complex B.

<Measurement of Light Emission Strength>

A thin film was prepared by spin coating 0.2wt % chloroform solution ofthe above polymeric light-emitting substance A on quartz. The lightemission spectrum of this thin film was measured using afluorospectrophotometer (produced by JOBIN YVON/SPEC Co., FL3-221 TAUfluorospectrophotometer). For calculation of light emission strength,the light emission spectrum excited at 350 nm was used. The relativevalue of light emission strength was determined by dividing the area oflight emission spectrum which was plotted on wave number as abscissas bythe absorbance at 350 nm. The measurement result is shown below. LightEmission Strength Light Emission Wavelength (nm) Relative Strength 4501.97 476 1.78 523 1.67

1. A metal complex which has a monovalent group having a metal complexstructure which represents light emission from triplet excited state,and represented by the following formula (1) or (2),

(wherein, A is a single bond or a divalent group derived from conjugatesystem. R¹ and R² each independently represent a halogen atom, alkylgroup, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group,arylalkylamino group, arylalkyl silyl group, acyl group, acyloxy group,imino group, amide group, arylalkenyl group, arylalkynyl group, cyanogroup, or a monovalent heterocyclic group. R³ represents alkyl group,aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or amonovalent heterocyclic group. a represents an integer of 0 to
 3. brepresents an integer of 0 to
 4. When a is two or more, a plurality ofR¹s may be the same or different. When b is two or more, a plurality ofR²s may be the same or different.)

(wherein, D is a single bond or a divalent group derived from conjugatesystem. R⁴ and R⁵ each independently represent a halogen atom, alkylgroup, alkoxy group, alkylthio group, alkylamino group, alkylsilylgroup, aryl group, aryloxy group, arylthio group, arylamino group,arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group,arylalkyl amino group, arylalkyl silyl group, acyl group, acyloxy group,imino group, amide group, arylalkenyl group, arylalkynyl group, cyanogroup, or a monovalent heterocyclic group. c and d each independentlyrepresent an integer of 0 to
 4. When c is two or more, a plurality ofR⁴s may be the same or different. When d is two or more, a plurality ofR⁵ may be the same or different.)
 2. A complex represented by the belowformula (3), and having phosphorescence in a visible region,

(wherein, M¹ is a metal which is an atom having an atomic number of 50or more, and intersystem crossing between a singlet state and a tripletstate can occur in this complex by spin-orbit interaction. L¹ representsa ligand represented by the following formula (4) or formula (5). L²represents: a ligand which bonds to M¹ by one or more of nitrogen atom,oxygen atom, carbon atom, sulfur atom, or phosphorus atom; a halogenatom; or a hydrogen atom. l represents an integer of 1-3. m representsan integer of 0-3. When l is two or more, a plurality of L¹s may be thesame or different. When m is two or more, a plurality of L²s may be thesame or different. l+m is an integer of 2-6.)

(wherein, Ar¹ represents a residue of a ligand which bonds to M¹ by oneor more of nitrogen atom, oxygen atom, carbon atom, sulfur atom, orphosphorus atom, and has covalent bonds to j pieces of As. j representsan integer of 1 to
 3. A, R¹ to R³, a, and b are the same as those of theabove formula (1).)

(wherein, Ar² represents a residue of a ligand which bonds to M¹ by oneor more of nitrogen atom, oxygen atom, carbon atom, sulfur atom, orphosphorus atom, and has covalent bonds to k pieces of Ds. k representsan integer of 1-3. D, R⁴, R⁵, c and d are the same as those of the aboveformula (2).).
 3. A complex according to claim 2, wherein L¹ is a ligandrepresented by the above formula (4).
 4. A complex according to claim 2,wherein L¹ is a ligand represented by the above formula (5), and D is adivalent group derived from conjugate system.
 5. A complex according toany one of claims 2 to 4, wherein L¹ bonds to M¹ by one or more nitrogenatoms, and/or one or more carbon atoms.
 6. A complex according to claim5, wherein L¹ is a multi-dentate ligand.
 7. A complex according to claim2, wherein Ar¹ or Ar² is a monovalent bidentate ligand represented bythe below formula (6) or (7),

(wherein, R⁶ to R¹³ each independently represent a hydrogen atom,halogen atom, alkyl group, alkoxy group, alkylthio group, alkylaminogroup, alkylsilyl group, aryl group, aryloxy group, arylthio group,arylamino group, arylsilyl group, arylalkyl group, arylalkoxy group,arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acylgroup, acyloxy group, imino group, amide group, arylalkenyl group,arylalkynyl group, cyano group, monovalent heterocyclic group, or agroup represented by the above formula (1) or formula (2). At least oneof R⁶ to R¹³ is a group represented by the above formula (1) or formula(2).)

(wherein, E¹ represents an oxygen atom or a sulfur atom. R¹⁴ to R¹⁹ eachindependently represent a hydrogen atom, halogen atom, alkyl group,alkoxy group, alkylthio group, alkylamino group, alkylsilyl group, arylgroup, aryloxy group, arylthio group, arylamino group, arylsilyl group,arylalkyl group, aryl alkoxy group, arylalkylthio group, arylalkylaminogroup, arylalkylsilyl group, acyl group, acyloxy group, imino group,amide group, arylalkenyl group, arylalkynyl group, cyano group,monovalent heterocyclic group, or a group represented by the aboveformula (1) or formula (2). At least one of R¹⁴ to R¹⁹ is a grouprepresented by the above formula (1) or formula (2).).
 8. A complexaccording to claim 2, wherein M¹ is an iridium atom, platinum atom, goldatom, or europium atom.
 9. An organic electroluminescent devicecomprising a layer which contains the complex according to claim 2between electrodes consisting of an anode and a cathode.
 10. A polymericlight-emitting substance wherein said light-emitting substance has ametal complex structure showing light emission from triplet excitedstate in the main chain or side chain, and has a monovalent grouprepresented by the above general formula (1) or (2).
 11. A polymericcompound according to claim 10, wherein said polymeric compoundcomprising a repeating unit represented by the below formula (8), (9) or(10), has phosphorescence in a visible region,

(wherein, M² is an atom having atomic number of 50 or more, spin-orbitinteraction occurs in the complex, and intersystem crossing between asinglet state and a triplet state can occur in the metal. L³ representsa ligand represented by the below formula (12) or (13). L⁴ represents: aligand which bonds to M² with one or or more of nitrogen atom, oxygenatom, carbon atom, sulfur atom, or phosphorus atom; a halogen atom; or ahydrogen atom. e represents an integer of 1-3. f represents an integerof 0-3. L⁵ is a ligand which bonds to M² with one or more of nitrogenatom, oxygen atom, carbon atom, sulfur atom, or phosphorus atom, and hastwo bonds connected to two neiboring repeating units with covalentbonding. When e is two or more, a plurality of L³ may be the same ordifferent. When f is two or more, a plurality of L⁴ may be the same ordifferent. e+f is an integer of 1-5.)

(wherein, Ar⁴ is a residue of the ligand which bonds to M² with one ormore nitrogen atom, oxygen atom, carbon atom, sulfur atom, or phosphorusatom, and bonds to o pieces of As. o represents an integer of 1-3. A,R¹-R³, a and b are respectively the same as those in the above formula(1).)

(wherein, Ar⁵ is a residue of the ligand which bonds to M² with one ormore nitrogen atom, oxygen atom, carbon atom, sulfur atom, or phosphorusatom, and has covalent bonds to p pieces of Ds. p represents an integerof 1-3. D, R⁴, R⁵, c, and d are respectively the same as those in theabove formula (2).)

(wherein, M², L³, and L⁴ are respectively the same as above. L⁶ and L⁷are each independently, a ligand which bonds to M² with one or morenitrogen atom, oxygen atom, carbon atom, sulfur atom, or phosphorusatom, and has a covalent bond to one neiboring repeating unit with onefree bond, respectively. g represents an integer of 1-3 and h representsan integer of 0-3. L³s may be the same or different. When h is two ormore, a plurality of L⁴s may be the same or different. g+h is an integerof 1-4.)

(wherein, M², L³, L⁴, e, and f are respectively the same as those in theabove formula (8). Ar³ is a trivalent aromatic group or a trivalentheterocyclic group. L⁸ is a ligand which bonds to M² with one or morenitrogen atom, oxygen atom, carbon atom, sulfur atom, or phosphorusatom, and has a covalent bond to Ar³ with one free bond.).
 12. Apolymeric compound according to claim 10, wherein said polymericcompound has a structure represented by the below formula (11) at thepolymer terminal, and has phosphorescence in a visible region.

(wherein, M², L³, L⁴, e, and f are respectively the same as those in theabove formula (8). L⁹ is a ligand which bonds to M² with one or morenitrogen atom, oxygen atom, carbon atom, sulfur atom, or phosphorusatom, and has a covalent bond at the polymer terminal with one freebond.)
 13. A polymeric compound according to claim 10, wherein saidpolymeric compound has a metal complex structure showing light emissionfrom triplet excited state, and has a monovalent group represented bythe above formula (1) or (2), on a repeating unit other than said metalcomplex structure.
 14. A polymeric compound according to any one ofclaims 10-13, wherein the main chain is a conjugated polymer.
 15. Apolymeric compound according to claim 14, wherein said polymericcompound comprises the repeating unit represented by the followinggeneral formula (14),

(wherein, Ar⁶ represents an arylene group or a divalent heterocyclicgroup. R²⁰ and R²¹ each independently represent a hydrogen atom, alkylgroup, aryl group, arylalkyl group, arylalkenyl group, arylalkynylgroup, monovalent heterocyclic group, or cyano group. At least one ofR²⁰, R²¹, or the substituents on Ar⁶, represents a group represented bythe above formula (1) or (2). n is 0 or 1.).
 16. A polymeric compoundaccording to claim 10, wherein at least one ligand of the metal complexportion showing light emission from triplet excited state bonds to ametal through a nitrogen atom and/or a carbon atom.
 17. A polymericcompound according to claim 10, wherein at least one ligand of the metalcomplex portion showing light emission from triplet excited state is amulti-dentate ligand.
 18. A polymeric compound according to claim 10,wherein at least one ligands of the metal complex portion showing lightemission from triplet excited state is a monovalent bi-dentate ligandrepresented by the below formula (15) or (16),

(wherein, R²² to R²⁹ each independently represent a hydrogen atom,halogen atom, alkyl group, alkoxy group, alkylthio group, alkylaminogroup, alkylsilyl group, aryl group, aryloxy group, arylthio group,arylamino group, aryl silyl group, arylalkyl group, arylalkoxy group,arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acylgroup, acyloxy group, imino group, amide group, arylalkenyl group,arylalkynyl group, cyano group, or monovalent heterocyclic group. Atleast one of R²² to R²⁹ is a free bond with a main chain or a sidechain.)

(wherein, E² represents an oxygen atom or a sulfur atom. R³⁰ to R³⁵ eachindependently represent a hydrogen atom, halogen atom, alkyl group,alkoxy group, alkylthio group, alkylamino group, alkylsilyl group, arylgroup, aryloxy group, arylthio group, arylamino group, arylsilyl group,arylalkyl group, aryl alkoxy group, arylalkylthio group, arylalkylaminogroup, arylalkylsilyl group, acyl group, acyloxy group, imino group,amide group, arylalkenyl group, arylalkynyl group, cyano group, ormonovalent heterocyclic. At least one of R³⁰ to R³⁵ is a free bond witha main chain or a side chain.).
 19. A polymeric compound according toclaim 10, wherein the central metal of the metal complex portion showinglight emission from triplet excited state is an iridium atom, platinumatom, gold atom, or europium atom.
 20. An organic electroluminescentdevice comprising a layer which contains the polymeric compoundaccording to claim 10 between electrodes consisting of an anode and acathode.